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ORGANIC PEROXIDES Organic Peroxides – Their Safe Handling and Use TABLE OF CONTENTS 1 SECTION PAGE INTRODUCTION 1 Introduction 2

2 Safety Guidelines/Sources of Hazard 3 The purpose of this bulletin is to Since organic peroxides are reactive provide information on the safe chemicals, they can be dangerous if 3 Hazard Information 4 handling and use of organic peroxides. mistreated or mishandled.

4 Description of Various Product Classes 8 Chemically, organic peroxides are compounds characterized by the pres- In case of Emergency call – 5 Storage 9 ence of an oxygen-oxygen linkage in Chemtrec: 800-424-9300 the molecular structure. 6 Disposal/Spillage 11 For Medical Assistance call – Organic peroxides are sensitive to heat R.M.P.C.C.: 303-623-5716 7 Packaging 12 and contamination, since these condi- (Rocky Mt. Poison Control Center) tions will cleave the oxy-oxy bonds to 8 Transportation 12 form free radicals.

9 First Aid 12 SAFETY GUIDELINES/TYPES 10 Safety Check List 13 2 OF ORGANIC PEROXIDES

11 Conclusion 14 A wide variety of organic peroxides There are differences in the degree are now offered commercially to meet and type of hazard associated with the sophisticated needs of polymer these peroxides. A series of tests has manufacturers. Among them are been carried out to evaluate proper- peroxyesters, peroxydicarbonates, ties such as shock sensitivity, heat dialkyl peroxides, diacyl peroxides, sensitivity, burning rate, flash point hydroperoxides, peroxyketals and and storage stability. The results of MEK peroxides. Products represent- the tests have proven helpful in ing each of these classes are listed in establishing safe handling, storage Table 1. (Note: MEK or Ketone perox- and disposal guidelines, and in devel- ides are a mixture of peroxides and oping the packaging and shipping hydroperoxides). procedures described in this bulletin.

Table 1 Representative organic peroxides

Peroxyesters Peroxydicarbonates Dialkyl Peroxides Diacyl Peroxides Hydroperoxides Peroxyketals Ketone Peroxides O O O O O R’OO OOR’

R-OOC-R R-OC-OO-CO-R R-OO-R R-C-OO-C-R R-OOH R-C-R Luperox P Luperox 223-M75S Luperox DI Luperox A98 Luperox TBH70X Luperox 231 Luperox DDM-9 (t-Butyl (Di-2-ethylhexyl (Di-t-Butyl peroxide) (Benzoyl peroxide) (t-Butyl hydroperoxide) (1,1-Di(t-Butyl peroxy) (MEKP Solution perbenzoate) peroxydicarbonate) 3,3,5-trimethyl in Plasticizer - cyclohexane) 9% Active Oxygen)

Luperox® 26 Luperox 225-M60S Luperox 101 Luperox LP Luperox CU90 Luperox 331M80 Luperox Delta-X9 (t-Butyl peroctoate) (Di-sec-Butyl 2,5-dimethyl-2,5-bis (Lauroyl (Cumene 1,1-Di (MEKP Solution peroxydicarbonate) (t-Butyl-peroxy) hexane peroxide) hydroperoxide) (t-Butyl peroxy) in Plasticizer - cyclohexane 9% Active Oxygen)

Luperox 11M75 Luperox DC Luperox DHD-9 (t-Butyl (Dicumyl peroxide) (MEKP Solution peroxypivalate) in Plasticizer - 9% Active Oxygen) Luperox 10M75 Luperox F Luperox 224 (t-Butyl peroxy (2,2-bis (t-butyl peroxy) (2,4 Pentanedione neodecanoate) diisopropylbenzene(s)) Peroxide Solution in Plasticizer)

Note: Lupersol® DDM-9*, DHD-9*, DDM-30* and Delta X-9* will change to Luperox and drop * during 2001. Formulations will not change. 2 Lupersol® and Luperox® are registered trademarks of Arkema Inc. 3 HAZARDS INFORMATION

The major causes of peroxide HAZARD OVERVIEW E R decomposition (sources of hazard) U Danger Red The three primary types of hazards to be T

A Zone Zone are Heat, Fire, Friction, Shock and R concerned with are flammability, heat sensitiv- E self heating P

Contamination. Examples of the M ity and contamination. E common sources of these include: T The following statements are provided violent Heat - Sunlight; loss of refrigeration; decomposition as general discussion for these types radiators; heating elements; hot SADT of hazards, as they relate to all organic peroxides. reaction vessels; heating ducts. Increased Assay Loss Zone A.Flammability Fire - Open flame; sparks. Recommended Storage All organic peroxides will burn vigorously, Friction - Mixing; pumping; grinding; Temperature and once ignited will be difficult to extinguish. Safe Zone traffic over spillage (which can The flammability of organic peroxides will generate heat). also be affected by the decomposition Shock - Dropping; impact during TIME products. When most peroxides begin to transportation (which can generate Figure 1 decompose they will generate vapors and heat). heat. Such vapors may be flammable and greatest effect on SADT are rate of could be the cause of an explosion. Contamination - Metal salts; amines; decomposition and heat loss from B.Heat Sensitivity acids; bases; polymerization acceler- the package. Figure 1 illustrates the All organic peroxides are sensitive to heat. If ator; transition metals; persulfates. impact of the SADT. a peroxide is heated above a certain The major safety characteristics B.Shock Sensitivity temperature (depending on the specific Arkema Inc. measures to A standard weight is dropped on a heat sensitivity of the peroxide itself) the determine the relative hazard of an small sample in an “impact tester”. rate of decompostion will increase in an organic peroxide include: shock The height of the fall required for the uncontrolled manner. This reaction can sensitivity, the amount of energy weight to decompose the product become violent, releasing large volumes of released during a decomposition, is a measure of its sensitivity to hot, flammable gasses. and flash point. Also measured are shock. Dry/pure Dibenzoyl peroxide The temperature at which this will occur the ease of burning, sensitivity to rate (Luperox® A98) is one of the few depends on the volume of the peroxide, of heat rise, thermal stability, self commercially available peroxides to the container and the period of time accelerating decompostion tempera- exhibit shock sensitivity in this test. the peroxide remains at that temperature. ture and ignition or autoignition The self accelerating decomposition characteristics. C.Flash Point The standard (closed cup) SETA temperature (SADT) test provides a STANDARD SAFETY TESTS flash test is now used. It is the measure of this hazard. Standard tests have been developed temperature at which the product In general, the best way to avoid decom- for determining the hazard of perox- vapors ignite on contact with an position due to heat is to scrupulously ides. The following is a list and open flame. adhere to the recommended storage description of these established tests: temperatures for each product. This is D.Thermal Stability Test particularly true for peroxides requiring A.SADT (Self Accelerating Results are determined by storing refrigerated storage. Decomposition Temperature) peroxide at a constant temperature The SADT test establishes the for a specified time. The results of C.Contamination lowest temperature at which a this test in terms of weight loss and Chemical contamination can accelerate peroxide, in its largest commerical assay are used as criteria for estab- decomposition of organic peroxides. package, will undergo self acceler- lishing storage temperature and Care should be taken to avoid all forms ating decomposition. The type of shelf life requirements. of contamination, particularly oxidizing decomposition and damage poten- and reducing agents and metal salts – tial are measured, and the severity Product descriptions and safety especially strong mineral acids. These of decomposition is determined. data for representative organic will initiate a rapid decomposition at The two parameters having the peroxide formulations are given normal ambient temperatures, while in tables 2 and 3. many heavy metals such as copper, iron, brass, etc. will have a similar effect over a longer period of time. 3 Table 2 Ambient Products & Safety Data

Max. Storage NFPA Code NFPA Code NFPA Code NFPA Code 3 Trade Peroxide Physical Temp 704 Health 704 Flamm. 704 Reactivity 432 Storage Name Name Form Diluent Assay (%) °F (C°) SADT Hazard ID. Hazard ID. Hazard ID. Class

Luperox® LP Dilauroyl Peroxide Solid NA 98.50% 27° C/80° F 51° C (65#ctn) 1 2 2 IV (110 lb.) Luperox A98 Dibenzoyl Peroxide Solid NA 98% 38° C/ 100° F 68° C (1#ctn.) 1 3 4 I (1lb.)

Luperox A75 Dibenzoyl Peroxide Solid Water 75% 38° C /100° F 71° C (25# ctn) 1 2 2 III (25 lb.) HAZARDS INFORMATION Luperox A75FP Dibenzoyl Peroxide Solid USP Grade Water 75% 38° C /100° F 71° C (25# ctn.) 1 2 2 III (25 lb.) Luperox A70S Dibenzoyl Peroxide Solid USP Grade Water 70% 38° C/100° F 82° C (50# ctn) 1 2 2 IV (25 lb. Luperox ANS55 Dibenzoyl Peroxide Paste Mixture BBP & filler 55% 38° C/100° F 54° C (50# ctn) 1 2 2 IV (350 lb.) Luperox ANS55P Dibenzoyl Peroxide Paste Mixture BBP & Filler 55% 38° C/100° F 54° C (50# ctn) 1 2 2 IV (350 lb.) DBP & Calcium Luperox AFR40 Dibenzoyl Peroxide Paste Misture STEARATE 40% 38° C/100° F 55° C (40# CTN) 1 2 2 IV (380 lb.) Tricresyl Luperox ATC50 Dibenzoyl Peroxide Paste Mixture Phosphate 50% 38° C/100° F NE NE NE NE NE Dicalcium Luperox ACP35 Dibenzoyl Peroxide Paste Mixture Phosphate 35% 38° C/100° F NE 1 0 0 V (100 lb.) Luperox P t-Butyl Perbenzoate Liquid Mixture NA 98% 38° C/100° F 63° C (40# ctn) 1 3 3 II (5 gal.) Luperox PAR70 t-Butyl Perbenzoate Liquid Mixture Aromatic 100 70% 38° C/100° F est 63° C (40# ctn) NE NE NE NE Luperox 7M75 t-Butyl peroxyacetate Liquid Mixture OMS 75% 38° C/100° F 79° C (7#ctn) 1 3 3 I (5 gal.) Luperox 7M50 t-Butyl peroxyacetate Liquid Mixture OMS 50% 38° C/100° F 85° C (7#ctn) NE NE NE NE 2,4 Pentanedione 4% Active 38° C/100° F Luperox 224 Peroxide Liquid NA Oxygen (prefer<85° F) 54°C(42#ctn) 2 1 1 (V 5 gal. lb.) Methyl Ethyl Ketone 9% Active IV (5 gal.) Luperox DDM-9 (red) Peroxide Liquid Mixture Plasticizer Oxygen 38° C/100° F 75° C (45# ctn) 3 2 2 for DMP prod Methyl Ethyl Ketone 5.5% Active IV (5 gal.) Luperox DDM-30 (red) Peroxide Liquid Mixture Plasticizer Oxygen 38° C/100° F >85° C (8#ctn) 3 2 2 for DMP prod Methyl Ethyl Ketone 9% Active IV (5 gal) Luperox DHD-9 (red) Peroxide Liquid Mixture Plasticizer Oxygen 38° C/100° F 85° C (8#ctn) 3 2 2 for DMP prod Methyl Ethyl Ketone 9% Active IV (5 gal.) Luperox Delta X-9 (red) Peroxide Liquid Mixture Plasticizer Oxygen 38° C/100° F 85° C (8#ctn) 3 2 2 for DMP prod MEKP & Cumene 8.6% Active Clear Catalyst 11* Hydroperoxide Liquid Mixture Plasticizer Oxygen (min) 38° C/100° F NE NE NE NE NE MEKP & Cumene 8.6% Active Red Catalyst 11* Hydroperoxide Liquid Mixture Plasticizer Oxygen (min) 38° C/100° F NE NE NE NE NE MEKP & Cumene 8.7% Active Catalyst 730* Hydroperoxide Liquid Mixture Plasticizer Oxygen (min) 38° C/100° F NE NE NE NE NE Luperox CU90 Cumene Hydroperoxide Liquid NA 88 to 90% 38° C/100° F 82° C (5 gal. ctn) 3 2 2 III (55 gal.) t-amyl peroxy-2- 38° C/100° F Luperox TAEC ethylhexyl carbonate Liquid NA 91% (prefer <85° F) 65° C (35#ctn) NE NE NE NE t-butyl peroxy-2- 38° C/100° F Luperox TBEC ethylhexyl carbonate Liquid NA 95% (prefer <85° F) 65°C(35#ctn) 1 3 2 III (5 gal.) t-butylperoxy isopropyl 38° C/100° F Luperox TBIC M75 carbonate Liquid Mixture OMS 75% (prefer <85° F) 65° C (35#ctn) 1 3 3 II (5 gal.) Luperox DI Di-t-butyl Peroxide Liquid NA >98% 38° C/100° F 80° C (30#ctn) 1 3 2 III (55 gal.) Luperox TBH 70X t-butyl Hydroperoxide Liquid Mixture Water 70% 38° C/100° F est. 88° C [35# ctn.] 3 2 2 IV (55 gal.) Luperox TBH 70 t-butyl Hydroperoxide Liquid Mixture DTBP 70% 38° C/100° F est. 88° C [35# ctn.] 3 3 3 II (55 gal.) Luperox 555M60 t-amyl peroxyacetate Liquid Mixture OMS 60% 38° C/100° F 75° C [35# ctn.] 2 3 2 III(5 gal.) Luperox TAP t-amyl peroxybenzoate Liquid NA 95% 38° C/100° F 65° C [40# ctn.] 2 3 2 II(5 gal.) Luperox DTA Di-t-amyl Peroxide Liquid NA 96% 38° C/100° F 75° C [30# ctn.] NE NE NE NE 2,5-Dimethyl 2,5 -Di Luperox 130 (t-butylperoxy) hexyne-3 Liquid NA 90 to 95% 38° C/100° F 93° C [35# ctn.] NE NE NE NE 2,5-Dimethyl 2,5 -Di Calcium Luperox 130XL45 (t-butylperoxy) hexyne-3 Solid Mixture Carbonate 45% 38° C/100° F 88° C [100# ctn.] NE NE NE NE 2,5-Dimethyl 2,5 -Di Luperox 101 (t-butylperoxy) hexane Liquid NA 91 to 93% 38° C/100° F 86° C [30# ctn.] 2 3 2 III (30 gal.) 2,5-Dimethyl 2,5 -Di Calcium Luperox® 101XL45 (t-butylperoxy) hexane Solid Mixture Carbonate 45% 38° C /100° F82° C [100# ctn.] 1 1 1 V (100 lb.) 2,5-Dimethyl 2,5 -Di Luperox HP101XLP (t-butylperoxy) hexane Solid MIxture Mixture 38° C /100° F est. 82° C [100# ctn.] NE NE NE NE 2,5-Dimethyl 2,5 -Di Luperox 101PP20 (t-butylperoxy) hexane Solid MIxture Polypropylene 20% 38° C /100° F est. 82° C [100# ctn.] NE NE NE NE

Di-2-t-butylperoxy Luperox F isopropyl benzene Liquid NA 97% 38° C /100° F NE 1 2 2 III (100 lb.) Di-2-t-butylperoxy Calcium Luperox F40P isopropyl benzene Liquid Carbonate 40% 38° C /100° F NE 1 1 0 V(100 lb.) Di-2-t-butylperoxy Luperox F40KE isopropyl benzene Solid Clay 40% 38° C /100° F NE 1 1 0 V(100 lb.)

Di-2-t-butylperoxy Luperox F40KEP isopropyl benzene Solid Clay 40% 38° C /100° F NE 1 1 0 V(100 lb.) Di-2-t-butylperoxy Luperox F40MG isopropyl benzene Solid EPM Rubber 40% 38° C /100° FNENENENENE Luperox DCSC Dicumyl Peroxide Solid NA 99% 38° C /100° F91° C [40# ctn.] 2 2 2 IV(55 gal.) Luperox DC40P Dicumyl Peroxide Solid Calcium Carbonate 40% 38° C /100° F NE 1 1 1 V(100 lb.) Luperox DC40KE Dicumyl Peroxide Solid Clay 40% 38° C /100° F NE 1 1 1 V(100 lb.) Luperox DC40KEP Dicumyl Peroxide Solid Clay 40% 38° C /100° F NE 1 1 1 V(100 lb.) Luperox DC40MG Dicumyl Peroxide Solid EPM Rubber 40% 38° C /100° FNENENENENE 1,1 Di(t-amylperoxy) Luperox 531M80 cyclohexane Liquid Mixture OMS 80% 32° C /90° F60° C [30# ctn.] 2 3 2 III(5 gal.) Ethyl 3,3 di- t-amyl Luperox 533M75 peroxy butyrate Liquid OMS 75% 32° C /90° F80° C [35# ctn.] 1 3 2 III(5 gal.) 1,1 di-t-(butylperoxy 3,3,5 trimethyl Luperox 231 cyclohexane Liquid NA 92% 32° C /90° F66° C [35# ctn.] 2 3 3 II(5 gal.) 1,1 di-t-(butylperoxy 3,3,5 trimethyl Luperox 231P75 cyclohexane Liquid Phthalate 75% 32 °C /90° F est. 66° C [35# ctn.] 2 3 3 II(5 gal.) 1,1 di-t-(butylperoxy 3,3,5 trimethyl Luperox 231XL40 cyclohexane Solid Calcium Carbonate 40% 32° C /90° F60° C [100# ctn.] 1 1 1 V(100 lb.) n-butyl 4,4 bis t-butyl Luperox 230XL40 peroxy valerate Solid Calcium Carbonate 40% 38° C /100° F60° C [20# ctn.] NE NE NE NE n-butyl 4,4 bis t-butyl Luperox 230 peroxy valerate Liquid NA 95 - 98% 38° C /100° F75° C [40# ctn.] 2 3 2 II (5 gal.) Ethyl 3,3 di- t-butyl Luperox 233M75 peroxy butyrate Liquid OMS 75% 38° C /100° F80° C [35# ctn.] 2 2 2 III(5 gal.) 1,1 Di(t-butylperoxy) 80% NE 65° C [35# cnt] Luperox 331M80 cyclohexane Liquid Mixture OMS 32° C /90° F for phthalate blend 1 3 3 II(5 gal.

NOTE: Lupersol® DDM-9*, DDM-30*, DHD -9* and Delta X-9* trade names are scheduled to change to those indicated in the table during 2000 or 2001. PRODUCT FORMULATIONS WILL NOT CHANGE. Table 3 Arkema Inc. Refrigerated Products

Trade Peroxide Physical Name Name Form Diluent Assay (%)

Luperox SAP succinic acid peroxide Frozen Solid Water 57.29 2-Hydroxy-1, 1-dimethyl Luperox 610M50 butylperoxyneodecanoate Liquid Mixture OMS 50% t-amyl peroxy -2-ethyl Luperox 575 hexanoate Liquid NA 95% Luperox 575M75 t-amyl peroxy -2-ethyl hexanoate Liquid Mixture OMS 75%

Luperox 11M75 t-butyl peroxypivalate Liquid Mixture OMS 75%

Luperox 11M45 t-butyl peroxypivalate Liquid Mixture OMS 45% t-butylperoxy Luperox 10 neodecanoate Liquid NA >99% t-butylperoxy Luperox 10M75 neodecanoate Liquid Mixture OMS 75% di-n-propyl Luperox 221 peroxydicarbonate Liquid NA >99% di-2-ethylhexyl Luperox 223S peroxydicarbonate Liquid NA >97% di-2-ethylhexyl Luperox 223M75S peroxydicarbonate Liquid Mixture OMS 75% di-sec-butyl Luperox 225S peroxydicarbonate Liquid NA >98% di-sec-butyl Luperox 225M60S peroxydicarbonate Liquid Mixture OMS 60% alpha-cumyl peroxy Luperox 188M75 neoheptanoate Liquid Mixture OMS 75% alpha-cumyl peroxy Luperox 288M75 neoheptanoate Liquid Mixture OMS 75% t-amyl Luperox 546M75 peroxyneodecanoate Liquid Mixture OMS 75% Luperox 554M75 t-amyl peroxypivalate Liquid Mixture OMS 75% Luperox 554M50 t-amyl peroxypivalate Liquid Mixture OMS 50% 2,5 dimethyl 2,5 bis-2- Luperox 256 ethyl hexanoyl peroxy hexane Liquid NA >90% Luperox DEC Didecanoyl peroxide Solid NA >98.5% t-butyl peroxy 2-ethyl Luperox 26 hexanoate Liquid NA >97% t-butyl peroxy 2-ethyl Luperox 26M50 hexanoate Liquid Mixture OMS 50% t-butyl peroxy 2-ethyl Luperox 26P50 hexanoate Liquid Mixture Phthalate 50% 1,1 Di(t-butylperoxy) Luperox M33 cyclohexane & t-butyl Liquid Mixture OMS 65% peroxy-2-ethylhexanoate

† Data referenced from NFPA 432 Code for the storage of REMARKS NOTES: organic peroxide formulations; 1997 edition. Luperox 223 M75S Possible phase separation below 0°F Rapid decomposition gives gasses which may OMS – odorless mineral spirits (–18°C). (C) spontaneously ignite in air. SADT – Self Accelerating Decompostion Temperature Luperox 11 M75 Freezes at -2°F (-19°C). Thawing at Phase separation and crystallization of solutions - Note: Lupersol® DDM-9*, DDM-30*, DHD-9* and Delta X-9* storage temperature returns to to return homogenous solution, let stand at recommended trade names are scheduled to change to those indicated in original form. storage temperature, with occasional mixing or shaking. the table during 2001. PRODUCT FORMULATIONS WILL NOT CHANGE.

6 Max. Storage NFPA Code NFPA Code NFPA Code NFPA Code Temp 704 Health 704 Flamm. Reactivity 432 Storage °F (C°) SADT Hazard ID.† Hazard ID.† Hazard ID.† Class†

32° F [0° C] 66° C [1# bag] NE NE NE NE

0° F [-18° C] 25° C [7# ctn] NE NE NE NE

50° F [10° C] 45° C [35# ctn] 0 3 2 III (55 gal.)

50° F [10° C] 45° C [35# ctn] NE NE NE NE 32° F [0° C] NOT <0° F (-18° C) 29° C [35# ctn] 2 3 3 II (5 gal.) 32° F [0° C] NOT <0° F (-18° C) 45° C [30# ctn] NE NE NE NE

14° F [-10° C] 21° C [30# ctn] NE NE NE NE

14° F [-10° C] 27° C [35# ctn] 2 3 2 III (5 gal.)

-10° F [-23° C] -7° C [9# ctn] 2 3 4 I (1 gal.)

0° F [-18° C] 15° C [8# ctn] 1 3 3 II (1 gal.)

14° F [-10° C] 20° C [7# ctn] NE NE NE NE

14° F [-10° C] 10° C [8# ctn] 1 3 3 II (1 gal.)

14° F [-10° C] 15° C [35# ctn] NE NE NE NE

5° F [-15° C] 15° C [37# ctn] 1 3 2 III (5 gal.)

0° F [-18° C] 20° C [35# ctn] 2 3 2 III (5 gal.)

14° F [-10° C] 25° C [30# ctn] 1 3 2 III (5 gal.) 20° F [-7° C] 30° C [30# ctn] 1 3 2 III (5 gal.) 20° F [-7° C] NE NE NE NE NE

60° F [16° C] 40° C [35# ctn] 0 3 2 III (5 gal.) 60° F [16° C] 43° C [50# ctn] 1 3 2 III (50 lb.)

50° F [10° C] 42° C [35# ctn] 1 3 2 III (5 gal.) III (55 gal.) 60° F [16° C] 54° C [30# ctn] 1 2 2 IV (5 gal.) III (55 gal.) 60° F [16° C] 65° C [7# ctn] 1 2 2 IV (5 gal.) NE 65°C [35# cnt] 15°C/59° F for phthalate blend NE NE NE NE

7 4 HAZARD OVERVIEW BY PEROXIDE FAMILY

Included below is information about C.PEROXYDICARBONATES Direct mixtures of the peroxide specific product classes, i.e., salient Peroxydicarbonates are thermally and the accelerator may decom- points about certain organic perox- unstable compounds. At their pose with violence and every ides in these groups as they relate recommended storage tempera- effort should be made to elimi- to these hazards as discussed in tures however they are not nate any possibility of direct section 3. expected to decompose. Above contact. Because of the wide the recommended storage range of contaminants which can PEROXIDE CLASSES temperatures, decomposition will interact with ketone peroxides, A.DIACYL PEROXIDES occur, and in some cases violent good housekeeping practices Dry benzoyl peroxide (Luperox® decomposition. should be strictly maintained. A98) is shock and friction sensi- Methyl Ethyl Peroxides should D.DIALKYL PEROXIDES tive. Except for Luperox A98, never be diluted with Acetone. Most Dialkyl peroxides have rela- commercial diacyl peroxides are tively high flash points, but once F. PEROXYKETALS formulated to be non-shock or ignited, will burn vigorously and Peroxyketals are extremely sensi- non-friction sensitive and must be are difficult to extinguish. tive to acid contamination which handled and stored properly. However, Di-t-Butyl Peroxide and causes rapid decomposition Examples include the wetted and Di-t-Amyl Peroxide have a low releasing flammable vapors which paste forms of benzoyl peroxide. flash point and their vapors are may self ignite. Wet forms of benzoyl peroxide highly flammable; thus, they must should not be allowed to dry out. G.HYDROPEROXIDES be handled as a flammable liquid Hydroperoxides are generally B.PEROXYESTERS as well as an organic peroxide. corrosive to skin and eyes. Peroxyesters are quite stable at Specific handling and use infor- Commercial formulations of their recommended storage mation are available upon request Hydroperoxides as supplied by temperatures. The recom- from Arkema Inc. Arkema Inc. are not shock mended temperatures for those E. KETONE PEROXIDES sensitive. Pure t-butyl hydroperoxide materials requiring refrigerated Ketone peroxides are corrosive to and 2,5-dihyroperoxy-2,5-dimethyl storage should be strictly eyes and irritants to skin. As a hexane are considered too shock adhered to ( consult Arkema group, the ketone peroxides are sensitive for commercial handling. Inc.’s Peroxyesters Product subject to decomposition through Hydroperoxides, in particular Bulletin). chemical action and are particu- cumene hydroperoxide, ( Luperox Some peroxyesters (such as larly sensitive to metallic salts. CU90) are sensitive to contamina- Luperox P) can freeze. Frozen They are widely used as room tion. Contact with incompatible materials can be thawed by plac- temperature catalysts for curing materials (such as strong acids ing in storage at recommended polyester resins which contain and strong oxidizers) can lead to a temperature. accelerators such as cobalt violent decomposition. naphthenate and cobalt/tertiary amine combinations.

8 5 STORAGE

In general, one of the most impor- 1. Comply with Federal, State and types of buildings are used depend- tant factors to observe when Local requirements. Consult ing on the storage requirement of working with organic peroxides is NFPA 432 for organic peroxide the peroxide and the amount that the required storage temperature. storage guidelines. will be stored, plus local fire codes, Exposure to a temperature that can insurance regulations and other laws. 2. Located in an isolated area. lead to an accelerated decomposi- A.Uncontrolled Temperature tion may result in the generation of 3. Used only for the storage of Storage flammable gasses and, in some organic peroxides. cases, spontaneous ignition. Products stored in this type of 4. Should be of fireproof construction. Proper storage is critical to the safe building do not normally require handling of organic peroxides, 5. Electrical equipment should be storage temperatures outside of particularly those requiring explosion proof: the normal ambient range (100˚F max.) to maintain assay, prevent controlled temperature storage. • Storage Areas = Class I self accelerating decomposition Ventilation is important because air Division II Group D circulation around peroxides stored and freezing. Uncontrolled at low temperatures reduces the • Process Areas = Class I temperature storage however chance of localized hot spots that Division I Group D should not exceed 100˚F. can cause decomposition. 6. Free of all combustible material. Depending on climate, buildings can be insulated, ventilated and/or Organic peroxide inventory should 7. Prevent exposure to sunlight. double walled. (See Figure 2) be rotated to avoid shelf life problems. Only minimal quantities of 8. Posted signs “Organic Peroxide B.Refrigerated Storage Facilities peroxide should be kept in the Storage” and “No Smoking”. Products stored in this type of immediate processing area. Freezer 9. For controlled temperature facility require lower than normal or refrigerated facilities should be peroxides, emergency back up ambient temperatures to preserve provided for intermediate storage of refrigeration should be installed. assay and to prevent self acceler- controlled temperature products. ating decomposition, e.g. chest 10. For controlled temperature per- type freezers. Note: It should be kept in mind that oxides, emergency sources of refrigerated storage facilities are dry ice should be locally available. C.Walk In Refrigerated Storage used to maintain low temperature Building peroxides at the required storage Large quantities of organic peroxides This type of facility is suitable for temperature and not for cooling should ideally be stored in specially storing large quantities of perox- low temperature peroxides to the designed buildings of non- ide which require refrigerated required temperature. Although combustible construction. conditions, e.g. Peroxydicarbo- NOT recommended by Arkema Detached buildings are the most nates. (See Figure 3) Inc., if only a portion of material common and preferred facilities for that is removed from refrigerated storing large quantities. Three basic storage is used, the remainder must be cooled to a temperature at, or Corrugated Alum. Rooﬁng somewhat below, the required temperature before being placed Plywood Air back into the refrigerated storage Air Out facilities. Failure to follow this proce- In dure could result in a serious Sun Shield on East, South & West Surfaces decomposition in the refrigerated storage area. Door Basic Guidelines Corrugated Alum. Corrugated All peroxide storage facilities should Plywood be designed along the following basic guidelines: Air In Figure 2

9 5 STORAGE

Figure 3 Walk-In Type Storage Unit Refrigerated storage building and key requirements, inside and out.

ORGANIC PEROXIDE

Organic Peroxide Diamond on each exterior wall. Safety release door opens with pressure. “Flammable Storage-Keep Fire Away” and “No Smoking” placards on outside of building. Temperature recorder and temperature alarm system (visual and audio). Metal portions of building should be grounded. Explosion-proof electrical equipment (Outside and Inside). Refrigeration units; Main and emergency backup systems (fluorocarbon type), located outside or away from building. For low-temperature peroxide storage (i.e. Lupersol® 223S, Luperox® 10M75) a liquid nitrogen fire protection system is recommended. Interior and exterior walls should be made of corrosion resistant design. Minimum insulation should be 3 inches of urethane for walls, ceiling and floor. Weather-proof covering and sun-shield over top of building. Inside evaporators; Main and emergency backup systems. Corrugated fiberglass on walls, pallets on floor, and spacing between rows of cartons; for air circulation.

Refrigerated Storage Building

10 6 SPILLAGE AND DISPOSAL

Organic peroxide spills must be more than 1% active oxygen, or no taken care of immediately. Spills more than 10% by weight (whichever can normally be handled by spread- is lower) in a satisfactory solvent ing an inert absorbent material is recommended. Fuel Oil #2 or directly on the spill, sweeping the non-flammable-polymerizable area and placing the sweepings in hydrocarbons (which are readily polyethylene bags for disposal. The soluble with the peroxide) are the sweepings should be wetted down most widely used solvents. Inciner- with water and disposed of immedi- ation can be accomplished after ately by an approved disposal satisfactory mixing. Incineration has method (see below). When all the the advantage of providing rapid material has been picked up, wash and complete decomposition along down the spill area with surfactant with the elimination of decomposi- and water to remove any traces of tion products. This method is not peroxide. Allow for sufficient ventila- generally recommended for disposal tion to aid in the removal of fumes of solid peroxides due to limited that may be present. solubility of solid peroxides with hydrocarbons. The following is the recommended method for disposal of organic Incineration must be performed in peroxides. accordance with all applicable Federal, State and Local regulations. DILUTION AND INCINERATION In general, an outside disposal Due to current environmental regula- company is used to perform tions, this method is quickly becoming this service. the most preferred for liquid peroxide disposal. Dilution of peroxide to no

11 7 PACKAGING 8 TRANSPORTATION

The containers in which organic Polyethylene is the preferred material Transportation regulations for organic peroxides are packaged include poly- since it is relatively inert and is flexible peroxide formulations are located ethylene bottles and jars, polyethylene enough to withstand normal pressure in the Code of Federal Regulations lined bags and fiber drums and buildup. Examples of typical containers (CFR); 49 CFR 173.225. specially coated steel drums. are shown below. Certain peroxides require refrigerated transportation as specified in 49 CFR 173.21(f)(3).

9 FIRST AID

Care should be exercised by all personnel handling organic peroxides. Acute hazards of organic peroxides may include skin/eye irritation, skin/eye corrositivity, and skin sensitization. Refer to MSDS or label for specific product health effects and first aid information. For immediate medical assistance contact the Rocky Mountain Poison Control Center at 303-623-5716.

12 10 SAFETY CHECK LIST

The following check list is provided as organic peroxide containers may be an cised to avoid any contamination. a summary in an attempt to avoid indication of imminent, possibly violent Clean, dry plastic or glass containers problems in the storage, handling or decomposition. should be used to transfer peroxide use of organic peroxides. The list is a samples. Dry ice should be available 7. Only minimal quantities of perox- basic safety and information guide, as to cool samples in an emergency. ides should be kept in the immediate it pertains to all organic peroxides. Direct heat should never be applied to processing area. organic peroxides. 1. Different classes of organic perox- 8. Avoid contact with incompatible ides have their own particular 17. As a rule, dilution of pure peroxides materials, such as oxidizers, reducing characteristics, specifications and with compatible solvents will increase agents, promoters, acids or bases. handling requirements. These are the safety characteristics of the perox- identified on the product labels and 9. The safe use of organic peroxides ides. described in the appropriate product demands that good housekeeping 18. Any spilled organic peroxides bulletins and MSDS. The product procedures be meticulously practiced. should be attended to immediately. label is designed to indicate recom- 10. Heat, flame, contamination, shock, Spills can normally be handled by mended storage temperature, specific friction and static electricity are poten- spreading an inert absorbent product hazard characteristics, special tial hazards when an organic peroxide substance directly on the spill, wetting handling information and appropriate is being charged to a reaction. Care with water, sweeping the area and first aid instructions. Product bulletins should be taken to eliminate or mini- then placing the sweepings in polyeth- provide chemical composition data, mize all of these. ylene bags for appropriate disposal. sales specifications (including shelf life), physical properties, and safety infor- 11. Contamination can be avoided by 19. Where spills occur, allow for suffi- mation, such as storage temperature using proper equipment and proper cient ventilation to aid in the removal of and SADT (Tables 2 and 3). materials of construction. Polymeric fumes that may be present. materials that may be soluble in 2. One of the most important factors 20. In disposing of organic peroxides, organic peroxide solutions should not to observe when working with an or the absorbent material that has be used as reaction vessels. organic peroxide is the recommended been used to remove spills, extreme Compatible materials of construction storage temperature. Exposure to a care should be exercised. The wetted include stainless steel 304 or 316 temperature that can lead to an acceler- absorbent material should be placed in (preferred), HDPE, polytetrafluorothy- ated decomposition may result in the a plastic bag and then incinerated. lene and glass linings. Do not use generation of flammable gasses, and in Federal, State and Local laws and copper, brass or iron. some cases spontaneous ignition. environmental regulations must be 12. Foreign materials, such as iron or observed in choosing a disposal 3. Refer to NFPA 432 for storage dirt, should be avoided when charging method. guidelines. Proper storage is critical to peroxides. the safe handling of organic peroxides, 21. The procedure for disposal of both those normally stored at ambient 13. Pumps used for organic peroxides empty peroxide containers must temperatures and those requiring must be “dedicated use” to avoid include a thorough draining and controlled temperature storage. potential contamination. should include rinsing with water or Ventilation is important because air a compatible solvent in particular for 14. Static buildup can be minimized by circulation around peroxides stored at refrigerated products. In accor- proper grounding and by keeping free low temperatures reduces the chance dance with Federal, State and local fall distances to a minimum, especially of localized hot spots that could cause regulation, these can then be sent when working with static sensitive decomposition. to an approved disposal site or initiators, such as dry benzoyl perox- incineration site. 4. Storage areas for peroxides should ide, and di-t-butyl peroxide. have explosion proof electrical equip- 22. Drum containers must always be 15. Friction caused by pumping ment. thoroughly flushed and drained before increases the temperature of the being sent to a reconditioner. 5. Organic peroxide inventories pumped solutions. Extra care should should be rotated to avoid shelf life be exercised when peroxide solutions 23. Cutting torches should never problems. are being re-circulated to avoid be used on empty peroxide drums. temperatures above SADT. Flammable vapors may be present. 6. Any observable gassing or distor- tion of the container, should be treated 16. When peroxide samples are used very carefully. Visible gassing of in analytical work, care should be exer-

13 11 CONCLUSION

A thorough understanding of the Responsible Care safety characteristics of organic Arkema Inc. is committed to peroxides is necessary in order to the ACC’s Responsible Care® and prevent accidents and to permit safe Product Stewardship initiatives. operations. The recommendations made in this Bulletin are presented as a service to aid in the safe handling, storage and disposal of organic peroxides. The safety tests described VISIT US ON THE WEB herein were used to establish safe www.Arkema-Inc.com handling procedures, packaging and shipping procedures for all organic peroxides. These guidelines are suggested to aid users of organic peroxide initiators. Available Safety Films 1. “Handle With Care” Discusses the hazards of peroxides storage and handling and offers recommended procedures. 2. “Keep It Cool and Keep It Clean” Considers hazards and preventa- tive measures relative to MEK peroxide use in unsaturated polyester applications. Other Information Sources • National Fire Protection Association (NFPA) www.nfpa.org 1-800-344-3555 NFPA 432 Code for the Storage of Organic Peroxide Formulations. • The Society of The Plastics Industry, Inc. (SPI) Organic Peroxide Producers Safety Division (OPPSD) www.plasticsindustry.org 1-202-974-5200 Safety and Handling of Organic Peroxides: A Guide (Publication #AS-109)

14 12 SAFE USE AND HANDLING OF AMBIENT ORGANIC PEROXIDE INITIATORS

1. Know the storage temperature and do not exceed it.

2. Know the SADT “Danger Temperature” and respect it.

3. Leave room for cool air circulation in storage area; follow the 2 foot rule.

4. Equip storage area properly.

5. Have fire extinguishers available.

6. Rotate inventory: “First In, First Out”.

7. Take only the amount that will be used.

8. Do NOT return unused initiator to storage buildings.

9. Rinse and slash containers prior to disposal.

10. Immediately clean up spills and dispose of them properly.

11. Protect your eyes and skin.

12. Use appropriate Personal Protective Equipment (PPE).

13. Initiator in large vessels should be diluted.

14. Know your plant’s emergency procedures.

Above all, when it comes to storing, handling and using organic peroxide initiators, “Don’t Lose Your Cool!” For additional information consult the Material Safety Data Sheet (MSDS).

Arkema Inc. • Fine Chemicals Group • Organic Peroxides 2000 Market Street, Philadelphia, PA 90103 Phones: (800) 558-5575 • Fax: (215) 419-7413 • 24-Hour Emergency (800) 424-9300 www.Arkema-Inc.com

15 RESPONSIBLE CARE®

Arkema Inc. is committed to the ACC’s Responsible Care and Pro duct Steward ship initiatives.

In Case of Emergency Call CHEMTREC at 1-800-424-9300

For Medical Assistance Call R.M.P.C.C. at 1-303-623-5716

© 2007 Arkema Inc. All ri ghts reserve d. IMPORTA NT: The statements, technical information and recommendations contained here in are believed to be accurate as of the date here of. Since the conditions and methods of use of the p roduct and of the information referre d to here in are beyond our contro l, Arkema expre ssly disclaims any and all liability as to any results obtained or arising fro m any use of the pro duct or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PART ICULAR PURPOSE, WARRANTY OF MERC HANTA BILITY, OR ANY OTHER WARRANTY, EXPRESS OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMAT ION PROVIDED HEREIN. The information p rovided here in re lates only to the specific pro duct designated and may not be applicable when such pro duct is used in combination with other materials or in any pro cess. The user should thoro ughly test any application before commerc ialization. Nothing contained here in should be taken as an inducement to infringe any patent and the user is advised to take app ropriate steps to be assure d that any pro posed use of the pro duct will not result in patent infringement.

®Lupero x, Lupersol, are registere d trademarks of Arkema Inc.

®Responsible Care is a registere d trademark of the American Chemistry Council

Arkema Inc. • 2000 Market St. • Philadelphia, PA 19103 • 1-800-558-5575 • Fax: 215-419-5671 • www. Arkema-Inc.com QC-1230 1M 1/01 LITHO IN U.S.A.