ORGANIC PEROXIDES / Polymer crosslinking

1 ORGANIC PEROXIDES / Polymer crosslinking23 The Arkema group is one of the main global producers of ORGANIC PEROXIDES . Its expertise also extend to glass coatings, additives for PVC, catalysts for synthesis in fine chemicals, polyester resins and specialty ORGANIC PEROXIDES activity, headquartered in King of Prussia (United States), operates facilities throughout the world. Its products, services and technical support are available to customers in Europe, North America, Asia, Africa and the Middle is building the future of the chemical industry using a responsible, innovation-based s leading chemicals producer, Arkema is aiming to become one of the global leaders in specialty chemicals. With its 14,000 employees and 91 industrial sites in 40 countries, Arkema has a revenue of Arkema group was created in October 2004, following the reorganization of Total s Chemicals branch. Thanks to innovation, targeted acquisitions and investments in emerging countries, it has become a recognized world player in the field of specialty NAMECHEMICAL NAMECHEMICAL FORMULAPRODUCT NAMEPHYSICAL FORMASSAY (%)ACTIVE OxYgENCARRIERUNSADTSTORAgE TEMPERATUREPACKAgINgTs maxTs minLUPEROX F1,3-1,4-bis(tert-butylperoxyisopropyl)b enzeneCas N 25155-25-3 Molecular weight: gMelting point: 37-54 CActive oxygen.

2 F Flakessolid flakes96 C30 C-20 kg bag in carton boxLUPEROX FreeOsolid flakes96 C30 C-20 kg bag in carton boxLUPEROX C40 C-25 kg in plastic binLUPEROX C30 C-20 kg bag in carton boxLUPEROX FreeO-40 LUPEROX F40 PLUPEROX F40 LUPEROX F40P-SP2granule carbonate + SilicaNRNRNR310680 C30 C-20 kg bag in carton boxLUPEROX F40 KEPLUPEROX C30 C-20 kg bag in carton boxLUPEROX F40 MGLUPEROX F40 MFLUPEROX C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX F40 MGEVTLUPEROX + EVA + SilicaNR80 C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX + Calcium carbonate + SilicaNR80 C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX F40 EDF sheetLUPEROX F40M-SPpelletLUPEROX DCPD icumyl peroxideCas N 80-43-3 Molecular weight: 270,4 gMelting point: > 39 CActive oxygen: DCPsolid crystals99 C30 C-20 kg bag in carton boxLUPEROX DC40P LUPEROX DC40 LUPEROX carbonate + Silica307780 C30 C-20 kg bag in carton boxLUPEROX DC40 KEPLUPEROX C30 C-20 kg bag in carton boxLUPEROX DC40 MGLUPEROX DC40 MFLUPEROX C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX DC40 MGFLUPEROX + Calcium carbonate + Silica307780 C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX DC40 MGPE pellet + LPDE307780 C30 C-25 kg bag in carton box20 kg bags in big boxLUPEROX C30 C-25 kg bag in carton boxLUPEROX 1012,5-dimethyl-2,5-di(tert-butylperoxy) hexaneCas N 78-63-7 Molecular weight: gMelting point: 8 CActive oxygen: 101liquid94 C30 C8 C25 kg in plastic binLUPEROX C30 C-20 kg bag in carton boxLUPEROX 101XL45 LUPEROX carbonate + Silica310875 C30 C-20 kg bag in carton boxLUPEROX 801 Tert-butylcumylperoxideCas N 3457-61-2 Molecular weight: gMelting point: CActive oxygen.

3 801liquid95 C30 C16 C25 kg in plastic binLUPEROX 1302,5-dimethyl-2,5-di(tertbutylperoxy)h ex-3-yneCas N 1068-27-5 Molecular weight: 286,42 gActive oxygen: : this product only exists as extended gradeLUPEROX oil310390 C30 C8 C25 kg in plastic binLUPEROX carbonate + Silica310690 C30 C-20 kg bag in carton boxLUPEROX 230n-butyl-4,4-di(tert-butylperoxy)valer ateCas N 995-33-5 Molecular weight: gActive oxygen: : this product only exists as extended gradeLUPEROX 230G40 granule carbonate + Sodium aluminium silicate310865 C30 C-20 kg bag in carton boxLUPEROX 230XL40 LUPEROX 230XL40-SPpowder carbonate + Silica310860 C30 C-20 kg bag in carton boxLUPEROX 2311,1-di(tert-butylperoxy)-3,3,5-trimet hylcyclohexaneCas N 6731-36-8 Molecular weight: gActive oxygen: : this product only exists as extended gradeLUPEROX 231G40 LUPEROX 231XL40 granule powder carbonate + Sodium aluminium silicate311057 C30 C-20 kg bag in carton boxLUPEROX carbonate + Silica311057 C30 C-20 kg bag in carton boxLUPEROX DCBPDi(2,4-dichlorobenzoyl) peroxideCas N 133-14-2 Molecular weight: gActive oxygen: oil310660 C35 C-25 kg in plastic binOrganic PEROXIDES prOduct range fOr crosslinking arkeMa, innOvative cheMistry p.

4 2/3 Product range for crosslinking p. 4/5 Kinetic p. 6/7 Processing p. 8 Scorch protection solution p. 9 Smell free solution p. 10/11 Application polymerscOntents 45 The half-life of a peroxide at any specified temperature is the time required at that temperature to affect a loss of one half of the peroxide s active oxygen data is essential for selecting the optimum peroxide for a specific time-temperature half-life data is generated by studying their thermal decomposition in various solvents at low polarity of the solvent used will influence the peroxide decomposition kinetics. Thus it is important to compare peroxide half-life data generated in the same solvent and at the same is possible to estimate the quantity of reacted ORGANIC peroxide as a function of time. In the following graphs various PEROXIDES are compared for an easy selection based on decomposition rate at given time/temperature curvesin n-decane or n-dodecane% remaining peroxide vs.

5 Timeat 180 c% remaining peroxide vs. timeat 160 c1101001 Min1 Hour10 Hours1,00010,000100,00010012014016018020 0220 Temperature ( C)Time (seconds)kinetic and half-life tiMedecOMpOsitiOn rate Luperox 130 Luperox 801 Luperox 101 Luperox F Luperox DCP Luperox 230 Luperox 231 Luperox 130 Luperox 801 Luperox 101 Luperox F Luperox DCPTime (minutes)0 %10 %20 %30 %40 %50 %60 %70 %80 %90 %100 %05101520% Remaining peroxide Luperox DCP Luperox 230 Luperox 231 Time (minutes)0 %10 %20 %30 %40 %50 %60 %70 %80 %90 %100 %05101520% Remaining Peroxidehigh teMperature curing ORGANIC perOxideslOw teMperature curing ORGANIC PEROXIDES kinetickinetic67 Luperox 101 Luperox F Luperox 801 Luperox DCP Luperox 230 Luperox 231 Luperox 801 Luperox F Luperox 101 Luperox DCP Luperox 230 Luperox 23113015017019021000:0005:0010:0015:0020 :0025:00T90 (min:s)Temperature ( C)These data were generated using an ODR2000E graph shows the cure time represented by T90, which is the time needed at a specific temperature to get 90% of the peroxide decomposed.

6 This key feature of the peroxide is to be taken into account when selecting the proper below data were generated using a Mooney viscometer. TS05 is the scorch time at the processing temperature (usually at the Polymer extrusion temperature). This value represents the time during which the vulcanizable compound can be safely processed before unwanted crosslinking or scorch takes place. TS05 is defined by the time needed at a specific temperature to obtain a 5 Mooney Unit increase in the viscosity as measured from the MV or minimum tiMescOrch tiMe 9011010013012015014017016000:0005:0010:0 015:0020:0025:00 Scorch Time TS05 (min:s)Temperature ( C)t90 vs. temperaturein an epdM compoundMooney scorch ts05 vs. temperaturein an epdM compoundExample: Typically, to phr of Luperox F are used in an EPM/EPDM formulated peroxide , this quantity has to be divided by the peroxide , 4 to 8 phr of Luperox F40 is the typical range of quantities used for an EPM/EPDM grades are used at same dosage rate as standard PEROXIDES .

7 Luperox F Luperox 101 Luperox 801 Luperox 231 Luperox DCP Luperox (N m)Quantity of peroxide (phr)These data were generated using an ODR2000E rheometer. MH (Nm) is a torque measurement which is proportional to the relative amount of crosslinking bonds created by the peroxide . It is an indication of the mechanical properties to be densitysuggested dOsage rate Of luperOx ORGANIC PEROXIDES in sOMe pOlyMers crosslinking efficiency in an epdM compound at 185 c(except for luperox 230 and 231 at 170 c)PHR OF ACTIVE SUbSTANCELUPEROx FLUPEROx DCPLUPEROx 101 LUPEROx 130 LUPEROx 801 LUPEROx 230 LUPEROx 231 LUPEROx DCbPLDPELow density - - - - density PolyethyleneLUPEROX - - - VAEthyl-Vinyl Acetate - - - - - - - - - - - - - - - - - - - - acrylonitrile - - - - - Butadiene Rubber - - - - - FreeO offers to footwear manufacturers an alternative to current technologies commonly used.

8 Sport shoes with soles made of expanded EVA are known for releasing a strong and persistent odour in manufacturing plants, as well as in retail outlets. This smell is due to the crosslinking agent and its VOCs (Volatile ORGANIC Compounds), in particular FreeO offers: small amounts of VOC released; no release of unpleasant odor; outstanding crosslinking effi ciency (up to 40% lower dosage); easy use thanks to its fl akes FreeO is a bis isopropyl benzene freeO: safer and OdOurless sOlutiOn fOr fOaMed eva Under typical working conditions ORGANIC peroxide decomposes in different molecules. Dicumyl peroxide decomposes in acetophenone (52% of total amount), cumyl alcohol and methane. Acetophenone is characterised by a strong and persistent smell. Luperox FreeO decomposes in molecules different in composition and properties. These decomposition products are considered neither smelling nor persistent volatiles. Luperox FreeO does not contain additives added to mask the free Thanks to its characteristics, Luperox FreeO is an excellent crosslinking agent for a large range of rubbers allowing reduction of peroxide consumption up to 37%.

9 Luperox FreeO is available as pure in fl akes form and it allows easy handling and easy weighing. Luperox FreeO-40 is the diluted version on calcium carbonate in granule cOst/perfOrMance features F40 @ 183 CF40 @ 183 CF40M-SP @ 186 CF40M-SP @ 186 CF40P-SP2 @ 190 CF40P-SP2 @ 190 C Luperox F40M-SP Luperox F40 EDTS05 (min:s)Solution to solve Scorch Issues, to improve qualityx 3x 2+ 12 CSolution to improve productivity00:0005:0010:0015:0020:0025: 0030:0035:0040:0045:0050:001151201251301 35140145150155160165 Temperature ( C)Arkema Scorch Protection technology is a unique technology that provides outstanding protection against scorch both at mixing and crosslinking temperatures. By increasing the scorch time during mixing and extrusion of the rubber compound, "SP" PEROXIDES are the right technology which allows: better process control; higher product quality; higher "SP2" peroxide is the ultimate generation of scorch protection, designed for very scorchy elastomers such as HNBR and very challenging curing conditions such as high injection molding temperature.

10 The Arkema Scorch protection system is an Arkema s prOtectiOn technOlOgy As it allows to work at higher process temperature without generating scorch, the Arkema Scorch Protection technology allows the increase of process speed leading to the increase of productivity in all applications, including extrusion and :2103:4300:2103:0000:2102:16ts2 at moulding temperature (min:s) t90 at moulding temperature (min:s)00:0000:0001:0002:0003:0004:0000: 0500:1000:1500:2000:2500:308 phr peroxide in epdM cOMpOundprOductivity increase Benefit crosslinking density test demonstrate that Luperox FreeO does provide the same crosslinking density at 37% lower loading, or higher crosslinking density at the same loading crosslinking efficiency density of eva foamed compound as function of peroxide dosageMH-ML ( )Dosage (phr) FreeO Dicumyl peroxideEquivalent crosslinking FreeO does generate 68% lower VOC than DCP. Luperox FreeO decomposition products are methane, acetone and ter-butanol, characterised by low boiling point.