ORGANIC PEROXIDES FOR POLYMER CROSSLINKING

Transcription

1 ORGANIC PEROXIDES FOR POLYMER CROSSLINKING CROSSLINKING PEROXIDES

2 Crosslinking Peroxides Range PEROXIDES PRODUCT NAME FORMULE A global chemical company and France s leading chemicals producer, Arkema is building the future of the chemical industry every day. Deploying a responsible, innovation-based approach, we produce state-of-the-art specialty chemicals that provide customers with practical solutions to such challenges as climate change, access to drinking water, the future of energy, fossil fuel preservation and the need for lighter materials. 1,3 1,4-Bis (tert-butylperoxyisopropyl)benzene Cas N Molecular weight: g Melting point: 41 C Active oxygen: 9.45% With operations in more than countries, 14,000 employees and seven research centers, Arkema generates annual revenue of 5.5 billion and holds leadership positions in all its markets with a portfolio of internationally recognized brands. The world is our inspiration. Dicumyl peroxide Cas N Molecular weight: g Melting point: 39 C Active oxygen: 5.92% 2,5-dimethyl-2,5-di (tert-butylperoxy)hexane Cas N Molecular weight: g Melting point: 5 C Active oxygen: 11.02% LUPEROX 801 LUPEROX 130 LUPEROX 230 LUPEROX 231 tert-butylcumylperoxide Cas N Molecular weight: g Melting point: 6 C Active oxygen: 7.68% 2,5-dimethyl-2,5-di(tertbutylperoxy) hex-3-yne Cas N Molecular weight: g Active oxygen: 11.17% Note : this product only exists as extended grade n-butyl-4,4 -di (tert-butylperoxy)valerate Cas N Molecular weight: g Active oxygen: 9.57% Note: this product exists only as extended grade 1,1 -di(tert-butylperoxy)-3,3,5 trimethylcyclohexane Cas N Molecular weight: g Active oxygen: 10.58% Note: this product exists only as extended grade 2 LUPEROX DCBP Di(2,4-dihlorobenzoyl) peroxide Cas N Molecular weight: g Active oxygen: 4.2% Note: this product only exists as extended grade

3 Liquid PURES PEROXIDES Solid INERT FLEGMATISED PEROXIDES Granules Powder MASTERBATCH POLYMER PREDISPERSION (300 microns filtered) Pellets Sheets PEROXIDE CONTENT % CARRIER UN SADT STANDARD PACKAGING FLAKES 96 min C CRUSHED 96 min C LUPEROX MIX (paste) <% - 90 C 25 kg bag in plastic bin 90P 90 Silica C P KE KEP Kaolin MG MGEVT ED MG-SP M-SP MF MFEVT EDF P-SP2 EPM EPM + EVA EPM+ EPM EPM min C LUPEROX DC LUPEROX DCKE LUPEROX DCKEP Kaolin LUPEROX DCMG LUPEROX DCMGF LUPEROX DCMGPE LUPEROX DCMG-SP2 LUPEROX DCM-SP2 EPM EPM+ EPM + LPDE EPM+ EPM -SP2 > C 25 kg in plastic bin HP 101XLP C 22.7 kg bag in carton box XL Silica C XL45 XL45-SP C C LUPEROX min C 25 kg in plastic bin LUPEROX 130MO85 85 White oil C 25 kg in plastic bin LUPEROX 130XL C LUPEROX 230G LUPEROX 230XL C LUPEROX 230XL-SP C LUPEROX 231G LUPEROX 231XL 3110 >60 C LUPEROX 231XL-SP C LUPEROX DCBP (paste) 50 silicone oil C 25 kg in plastic bin 3

4 Kinetic Data / Half-Life 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 content. Half-life data is essential for selecting the optimum initiator for a specific time-temperature combination. Peroxide half-life data is generated by studying their thermal decomposition in various solvents at low concentrations. The 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 concentration. Half life Time Temperature Curves in n-decane or n-dodecane 100, Hours 10,000 1 Hour 1,000 LUPEROX Min LUPEROX LUPEROX 230 LUPEROX Temperature ( C) 4

5 Kinetic Data / Peroxide Decomposition Rate It 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 temperatures. HIGH TEMPERATURE CURING ORGANIC PEROXIDES % Remaining Peroxide vs. Time at 1 100% 90% 80% 70% 60% 50% LUPEROX 130 % LUPEROX % 20% 10% 0% (min) LOW TEMPERATURE CURING ORGANIC PEROXIDES % Remaining Peroxide vs. Time at 160 C 100% 90% 80% 70% 60% 50% % 30% 20% LUPEROX % LUPEROX 231 0% (min)

6 Aspect / Physical form Masterbatch in pellets Granules Free-flowing Powder Crystals 6

7 Selection / Suggested mixing technology masterbatches liquid granules powders soaking of polymer pellets internal mixer open mill direct peroxide injection direct screw compounding without injection Selection / Why to use masterbatch Experiments were performed with an EPDM compound in a Brabender type internal mixer. Standard deviation of MH was determined using an ODR2000E rheometer after different times of compounding. The times reported in this graph are the mixing times required to obtain an acceptable standard deviation in MH from batch to batch, comparing the various commercially available forms of di-(t-butylperoxy) diisopropylbenzene. Compounding time (s) Pre-dispersed peroxide masterbatches dramatically shorten mixing time and improve the quality of the elastomer by avoiding premature crosslinking or scorch in hard or soft compounds. The final elastomeric composition exhibits a desirably lower and more consistent viscosity, essential to molding and extrusion operations. Masterbatch peroxides are preferred in technical rubber articles production because they provide uniform peroxide dispersion and consistent physical properties Soft compounds shore A < 55 Hard compounds shore A > 55 Soft compounds shore A < 55 Hard compounds shore A > 55 Soft compounds shore A < 55 Hard compounds shore A > 55 Soft compounds shore A < 55 Hard compounds shore A > 55 7

8 Crosslinking density This data was 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 expected. Crosslinking efficiency in an EPDM compound at 185 C (except for LUPEROX 230 and 231 : 170 C) M H (Nm) LUPEROX LUPEROX Quantity of Peroxide (phr) LUPEROX 231 Suggested dosage rate of LUPEROX Organic Peroxides in some polymers phr of active substance LDPE Low Density Polyethylene HDPE High Density Polyethylene EVA Ethyl-Vinyl Acetate EPM/EPDM Ethylene-Propylene Monomers CM Chlorinated polyethylene Q Silicone rubbers NBR Butadiene acrylonitrile rubber SBR Styrene Butadiene Rubber LUPEROX 130 LUPEROX 801 LUPEROX 230 LUPEROX 231 LUPEROX DCBP LUPEROX MIX Example: Typically, 1.6 to 3.2 phr of Luperox F are used in an EPM/EPDM compound. For formulated peroxide, this quantity has to be divided by the peroxide content. Therefore, 4 to 8 phr of is the typical range of quantities utilized for an EPM/EPDM compound. SP grades are used at same dosage rate as standard peroxides. 8

9 Cure time This graph shows the cure time represented by T90, which is the time needed at a specific temperature to get 90% of the peroxide decomposed. This key feature of the peroxide is to be taken into account when selecting the proper peroxide. T 90 vs Temperature in an EPDM compound 25:00 20:00 LUPEROX 801 T90 (min:s) 15:00 10:00 05:00 LUPEROX : Temperature ( C) LUPEROX 231 Scorch Time The below data was 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 viscosity. Mooney Scorch T S05 vs Temperature in an EPDM compound LUPEROX 801 Scorch Time T S05 (min:s) 25:00 20:00 15:00 10:00 05:00 LUPEROX : Temperature ( C) LUPEROX 231 9

10 Solution for Scorch Protection Our Scorch Protection technology provides an outstanding protection against scorch both at mixing and cross-linking temperatures. SP is the right technology for increasing the scorch time during mixing and extrusion of rubber compounds for a better process safety. SP2 is the ultimate generation of Scorch Protected grade, designed for very scorchy elastomers such as HNBR and/or for very challenging curing conditions (high injection molding temperatures). 50:00 45:00 :00 Solution to solve Scorch Issues, to improve quality 35:00 30:00 ts05 (min:s) 25:00 20:00 x 3 Solution to improve productivity 15:00 10:00 x 2 M-SP 5:00 ED +12 C 0: Temperature ( C) Productivity increase When there is no scorch issue, the Scorch Protection technology allows an increase in processing speed without any scorch issue, leading to a productivity increase that could be interesting in all applications, extrusion and moulding. In the example below, the injection temperature has been adjusted to get exactly the same scorch time. 8 phr peroxide Elastomer: EPDM Dutral TER 49 T S2 at moulding temperature (min:s) 0:30 4:30 T 90 at moulding temperature (min:s) 0:20 0:10 0:00 00:21 00:21 00:21 3:43 3:00 2:16 1:00 0:00 F@183 C FM-SP@186 C FP-SP2@190 C F@183 C FM-SP@186 C FP-SP2@190 C 3:00 2:00 The consequence of this increase in moulding temperature is the significant decrease in cure time (T 90) with a 20% shorter cure time with FM-SP and a % shorter cure time with FP-SP2. 10

11 Application Polymers that can be crosslinked ABS Acrylonitrile butadiene styrene copolymer AU/EU Polyurethane rubber BR CM CR CSM EBA EPM EPDM EVA FKM HNBR IR NBR PE POE Q SBR T EEA Polybutadiene rubber Chlorinated polyethylene Polychloroprene rubber Chlorosulfonyl polyethylene Ethylene butylacrylate copolymer Ethylene propylene copolymer Ethylene propylene diene terpolymer Ethylene vinylacetate copolymer Fluoro rubber Hydrogenated butadiene acrylonitrile rubber Polyisoprene rubber Butadiene acrylonitrile rubber Natural rubber Polyethylene Polyolefin elastomer Silicone rubber Styrene butadiene rubber Polysulfide rubber Ethylene ethyl acrylate Polymers that cannot be crosslinked ACM Polyacrylate rubber CIIR Chlorobutyl rubber CO Epichlorohydrin rubber ECO Epichlorohydrin copolymer IIR Butyl rubber PB Polybutene-1 PIB Polyisobutene PVC Polyvinylchloride PP Polypropylene

12 EUROPE Arkema 420, rue d Estienne d Orves COLOMBES Cedex France Tél. : 33 (0) Fax : 33 (0) USA Arkema Inc Market Street PHILADELPHIA, PA USA Tel. : The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof. Since the conditions and methods of use of the product and of the information referred to herein are beyond our control, Arkema expressly disclaims any and all liability as to any results obtained or arising from any use of the product or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY OR ANY OTHER WARRANTY, EXPRESS OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein relates only to the specific product designated and may not be applicable when such product is used in combination with other materials or in any process. The user should thoroughly test any application before commercialization. Nothing contained herein constitutes a license to practice under any patent and it should not be construed as an inducement to infringe any patent and the user is advised to take appropriate steps to be sure that any proposed use of the product will not result in patent infringement. See MSDS for Health & Safety Considerations. The information contained in this document is based on trials carried out by our Research Centres and data selected from the literature, but shall in no event be held to constitute or imply any warranty, undertaking, express or implied commitment from our part. Our formal specifications define the limit of our commitment. No liability whatsoever can be accepted by Arkema with regard to the handling, processing or use of the product or products concerned which must in all cases be employed in accordance with all relevant laws and/or regulations in force in the country or countries concerned. 420, rue d Estienne d Orves Colombes - France Tél. : 33 (0) Fax : 33 (0) ARKEMA - société anonyme au capital de euros RCS Nanterre DIRCOM - 41E / /10 - Addi - Photos : ARKEMA - Conception : DUFOUR COMMUNICATION