ORGANIC PEROXIDES

Organic Peroxides –Their Safe Handling and Use

The purpose of this bulletin is toprovide information on the safehandling and use of organic peroxides.

Chemically, organic peroxides arecompounds characterized by the pres-ence of an oxygen-oxygen linkage inthe molecular structure.

Organic peroxides are sensitive to heatand contamination, since these condi-tions will cleave the oxy-oxy bonds toform free radicals.

Since organic peroxides are reactivechemicals, they can be dangerous ifmistreated or mishandled.

In case of Emergency call –Chemtrec: 800-424-9300

For Medical Assistance call –R.M.P.C.C.: 303-623-5716(Rocky Mt. Poison Control Center)

TABLE OF CONTENTS

SECTION PAGE

1 Introduction 2

2 Safety Guidelines/Sources of Hazard 3

3 Hazard Information 4

4 Description of Various Product Classes 8

5 Storage 9

6 Disposal/Spillage 11

7 Packaging 12

8 Transportation 12

9 First Aid 12

10 Safety Check List 13

11 Conclusion 14

INTRODUCTION1

A wide variety of organic peroxidesare now offered commercially to meetthe sophisticated needs of polymermanufacturers. Among them areperoxyesters, peroxydicarbonates,dialkyl peroxides, diacyl peroxides,hydroperoxides, peroxyketals andMEK peroxides. Products represent-ing each of these classes are listed inTable 1. (Note: MEK or Ketone perox-ides are a mixture of peroxides andhydroperoxides).

There are differences in the degreeand type of hazard associated withthese peroxides. A series of tests hasbeen carried out to evaluate proper-ties such as shock sensitivity, heatsensitivity, burning rate, flash pointand storage stability. The results ofthe tests have proven helpful inestablishing safe handling, storageand disposal guidelines, and in devel-oping the packaging and shippingprocedures described in this bulletin.

SAFETY GUIDELINES/TYPES OF ORGANIC PEROXIDES

2

Peroxyesters Peroxydicarbonates Dialkyl Peroxides Diacyl Peroxides Hydroperoxides Peroxyketals Ketone PeroxidesO 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 Pentanedioneneodecanoate) diisopropylbenzene(s)) Peroxide Solution

in Plasticizer)

Table 1 Representative organic peroxides

2Note: Lupersol® DDM-9*, DHD-9*, DDM-30* and Delta X-9* will change to Luperox and drop * during 2001. Formulations will not change.

Lupersol® and Luperox® are registered trademarks of Arkema Inc.

3

HAZARDS INFORMATION3

The major causes of peroxidedecomposition (sources of hazard)are Heat, Fire, Friction, Shock andContamination. Examples of thecommon sources of these include:

Heat - Sunlight; loss of refrigeration;radiators; heating elements; hotreaction vessels; heating ducts.

Fire - Open flame; sparks.

Friction - Mixing; pumping; grinding;traffic over spil lage (which can generate heat).

Shock - Dropping; impact duringtransportation (which can generateheat).

Contamination - Metal salts; amines;acids; bases; polymerization acceler-ator; transition metals; persulfates.

The major safety characteristicsArkema Inc. measures todetermine the relative hazard of anorganic peroxide include: shocksensitivity, the amount of energyreleased during a decomposition,and flash point. Also measured arethe ease of burning, sensitivity to rateof heat rise, thermal stability, selfaccelerating decompostion tempera-ture and ignition or autoignitioncharacteristics.

STANDARD SAFETY TESTSStandard tests have been developedfor determining the hazard of perox-ides. The following is a list anddescription of these established tests:

A.SADT (Self AcceleratingDecomposition Temperature)The SADT test establishes thelowest temperature at which aperoxide, in its largest commericalpackage, will undergo self acceler-ating decomposition. The type ofdecomposition and damage poten-tial are measured, and the severityof decomposition is determined.The two parameters having the

greatest effect on SADT are rate ofdecomposition and heat loss fromthe package. Figure 1 illustrates theimpact of the SADT.

B.Shock SensitivityA standard weight is dropped on asmall sample in an “impact tester”.The height of the fall required for theweight to decompose the productis a measure of its sensitivity toshock. Dry/pure Dibenzoyl peroxide(Luperox® A98) is one of the fewcommercially available peroxides toexhibit shock sensitivity in this test.

C.Flash PointThe standard (closed cup) SETAflash test is now used. It is thetemperature at which the productvapors ignite on contact with anopen flame.

D.Thermal Stability TestResults are determined by storingperoxide at a constant temperaturefor a specified time. The results ofthis test in terms of weight loss andassay are used as criteria for estab-lishing storage temperature andshelf life requirements.

Product descriptions and safetydata for representative organicperoxide formulations are given in tables 2 and 3.

SADT

ER UTAR EPMET

TIME

Increased Assay Loss Zone

Safe Zone

RecommendedStorage

Temperature

RedZone

violentdecomposition

DangerZone

self heating

Figure 1

HAZARD OVERVIEWThe three primary types of hazards to beconcerned with are flammability, heat sensitiv-ity and contamination.

The following statements are provided as general discussion for these types of hazards, as they relate to all organic peroxides.

A.FlammabilityAll organic peroxides will burn vigorously,and once ignited will be difficult to extinguish.

The flammability of organic peroxides willalso be affected by the decompositionproducts. When most peroxides begin todecompose they will generate vapors andheat. Such vapors may be flammable andcould be the cause of an explosion.

B.Heat SensitivityAll organic peroxides are sensitive to heat. Ifa peroxide is heated above a certaintemperature (depending on the specificheat sensitivity of the peroxide itself) therate of decompostion will increase in anuncontrolled manner. This reaction canbecome violent, releasing large volumes ofhot, flammable gasses.

The temperature at which this will occurdepends on the volume of the peroxide,the container and the period of time the peroxide remains at that temperature.The self accelerating decompositiontemperature (SADT) test provides ameasure of this hazard.

In general, the best way to avoid decom-position due to heat is to scrupulouslyadhere to the recommended storagetemperatures for each product. This isparticularly true for peroxides requiringrefrigerated storage.

C.ContaminationChemical contamination can acceleratedecomposition of organic peroxides. Care should be taken to avoid all forms of contamination, particularly oxidizing and reducing agents and metal salts –especially strong mineral acids. These will initiate a rapid decomposition at normal ambient temperatures, while many heavy metals such as copper, iron,brass, etc. will have a similar effect over alonger period of time.

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30(t-

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Liqu

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NENE

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2,5

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Calci

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XL45

(t-bu

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3So

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[100

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Lupe

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01(t-

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pero

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3%38

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32

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HAZARDS INFORMATION3

Tab

le 2

Am

bie

nt

Pro

ducts

& S

afe

ty D

ata

2,5-

Dim

ethyl

2,5

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Calci

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x®10

1XL4

5(t-

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82°

C [1

00#

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11

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P101

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Solid

MIxt

ure

Mixt

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38°

C /1

00°

Fes

t. 82°

C [1

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tn.]

NENE

NENE

2,5-

Dim

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2,5

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Lupe

rox 1

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20(t-

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2°C

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NE

Di-2

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Lupe

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isopr

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Liqu

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97%

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12

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(100

lb.)

Di-2

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Calci

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Piso

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11

0V(

100

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Di-2

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Lupe

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Clay

40%

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100

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Lupe

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Lupe

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NENE

NENE

NE

Lupe

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CSC

Dicu

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Pero

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Solid

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91°

C [4

0# ct

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22

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(55

gal.)

Lupe

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C40P

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Pero

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Solid

Calci

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38°

C /1

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11

1V(

100

lb.)

Lupe

rox D

C40K

EDi

cum

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roxid

eSo

lidCl

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11

V(10

0 lb

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Lupe

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C40K

EPDi

cum

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roxid

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11

V(10

0 lb

.)

Lupe

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C40M

GDi

cum

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roxid

eSo

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M R

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%38

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NENE

NENE

NE

1,1

Di(t-

amylp

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pero

x 531

M80

cyclo

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Mixt

ure

OMS

80%

32°

C /9

0°F

60°

C [3

0# ct

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23

2III

(5 g

al.)

Ethy

l 3,3

di-

t-am

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x 533

M75

pero

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utyr

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quid

OMS

75%

32°

C /9

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80°

C [3

5# ct

n.]

13

2III

(5 g

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1,1

di-t-

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3,3,

5 tri

meth

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x 231

cyclo

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33

II(5

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1,1

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meth

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x 231

P75

cyclo

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6°C

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23

3II(

5 ga

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1,1

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F60

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# ctn

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11

V(10

0 lb

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n-bu

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30XL

40pe

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lcium

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C [2

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NENE

NENE

n-bu

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is t-b

utyl

Lupe

rox 2

30pe

roxy

valer

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NA95

- 98

%38

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75°

C [4

0# ct

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23

2II

(5 g

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Ethy

l 3,3

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M75

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Trade Peroxide PhysicalName Name Form Diluent Assay (%)

Luperox SAP succinic acid peroxide Frozen Solid Water 57.292-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-ethylLuperox 26 hexanoate Liquid NA >97%

t-butyl peroxy 2-ethylLuperox 26M50 hexanoate Liquid Mixture OMS 50%

t-butyl peroxy 2-ethylLuperox 26P50 hexanoate Liquid Mixture Phthalate 50%

1,1 Di(t-butylperoxy) Luperox M33 cyclohexane & t-butyl Liquid Mixture OMS 65%

peroxy-2-ethylhexanoate

Table 3 Arkema Inc. Refrigerated Products

† Data referenced from NFPA 432 Code for the storage oforganic peroxide formulations; 1997 edition.

OMS – odorless mineral spiritsSADT – Self Accelerating Decompostion Temperature

Note: Lupersol® DDM-9*, DDM-30*, DHD-9* and Delta X-9*trade names are scheduled to change to those indicated inthe table during 2001. PRODUCT FORMULATIONS WILLNOT CHANGE.

REMARKS

Luperox 223 M75S Possible phase separation below 0°F(–18°C). (C)

Luperox 11 M75 Freezes at -2°F (-19°C). Thawing at storage temperature returns to original form.

NOTES:

Rapid decomposition gives gasses which may spontaneously ignite in air.

Phase separation and crystallization of solutions - to return homogenous solution, let stand at recommended storage temperature, with occasional mixing or shaking.

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 NE32° 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

Included below is information aboutspecific product classes, i.e., salientpoints about certain organic perox-ides in these groups as they relateto these hazards as discussed insection 3.

PEROXIDE CLASSES

A.DIACYL PEROXIDESDry benzoyl peroxide (Luperox®

A98) is shock and friction sensi-tive. Except for Luperox A98,commercial diacyl peroxides areformulated to be non-shock ornon-friction sensitive and must behandled and stored properly.Examples include the wetted andpaste forms of benzoyl peroxide.Wet forms of benzoyl peroxideshould not be allowed to dry out.

B.PEROXYESTERSPeroxyesters are quite stable attheir recommended storagetemperatures. The recom-mended temperatures for thosematerials requiring refrigeratedstorage should be strictlyadhered to ( consult Arkema Inc.’s Peroxyesters ProductBulletin).

Some peroxyesters (such asLuperox P) can freeze. Frozenmaterials can be thawed by plac-ing in storage at recommendedtemperature.

C.PEROXYDICARBONATESPeroxydicarbonates are thermallyunstable compounds. At theirrecommended storage tempera-tures however they are notexpected to decompose. Abovethe recommended storagetemperatures, decomposition willoccur, and in some cases violentdecomposition.

D.DIALKYL PEROXIDESMost Dialkyl peroxides have rela-tively high flash points, but onceignited, will burn vigorously andare diff icult to extinguish.However, Di-t-Butyl Peroxide andDi-t-Amyl Peroxide have a lowflash point and their vapors arehighly flammable; thus, they mustbe handled as a flammable liquidas well as an organic peroxide.Specific handling and use infor-mation are available upon requestfrom Arkema Inc.

E. KETONE PEROXIDESKetone peroxides are corrosive toeyes and irritants to skin. As agroup, the ketone peroxides aresubject to decomposition throughchemical action and are particu-larly sensitive to metallic salts.They are widely used as roomtemperature catalysts for curingpolyester resins which containaccelerators such as cobaltnaphthenate and cobalt/tertiaryamine combinations.

Direct mixtures of the peroxideand the accelerator may decom-pose with violence and everyeffort should be made to elimi-nate any possibil ity of directcontact. Because of the widerange of contaminants which caninteract with ketone peroxides,good housekeeping practicesshould be strictly maintained.Methyl Ethyl Peroxides shouldnever be diluted with Acetone.

F. PEROXYKETALSPeroxyketals are extremely sensi-tive to acid contamination whichcauses rapid decompositionreleasing flammable vapors whichmay self ignite.

G.HYDROPEROXIDESHydroperoxides are generallycorrosive to skin and eyes.Commercial formulations ofHydroperoxides as supplied byArkema Inc. are not shocksensitive. Pure t-butyl hydroperoxideand 2,5-dihyroperoxy-2,5-dimethylhexane are considered too shocksensitive for commercial handling.Hydroperoxides, in particularcumene hydroperoxide, ( LuperoxCU90) are sensitive to contamina-tion. Contact with incompatiblematerials (such as strong acidsand strong oxidizers) can lead to aviolent decomposition.

HAZARD OVERVIEW BY PEROXIDE FAMILY4

8

In general, one of the most impor-tant factors to observe whenworking with organic peroxides isthe required storage temperature.Exposure to a temperature that canlead to an accelerated decomposi-tion may result in the generation offlammable gasses and, in somecases, spontaneous ignit ion.Proper storage is critical to the safehandling of organic peroxides,particularly those requir ingcontrolled temperature storage.Ventilation is important because aircirculation around peroxides storedat low temperatures reduces thechance of localized hot spots thatcan cause decomposition.

Organic peroxide inventory shouldbe rotated to avoid shelf life prob-lems. Only minimal quantities ofperoxide should be kept in theimmediate processing area. Freezeror refrigerated facilities should beprovided for intermediate storage ofcontrolled temperature products.

Note: It should be kept in mind thatrefrigerated storage facilities areused to maintain low temperatureperoxides at the required storagetemperature and not for coolinglow temperature peroxides to therequired temperature. AlthoughNOT recommended by ArkemaInc., if only a portion of materialthat is removed from refrigeratedstorage is used, the remainder mustbe cooled to a temperature at, orsomewhat below, the requiredtemperature before being placedback into the refrigerated storagefacilities. Failure to follow this proce-dure could result in a seriousdecomposition in the refrigeratedstorage area.

Basic GuidelinesAll peroxide storage facilities shouldbe designed along the followingbasic guidelines:

1. Comply with Federal, State andLocal requirements. ConsultNFPA 432 for organic peroxidestorage guidelines.

2. Located in an isolated area.

3. Used only for the storage oforganic peroxides.

4. Should be of fireproof construction.

5. Electrical equipment should beexplosion proof:

• Storage Areas = Class IDivision II Group D

• Process Areas = Class IDivision I Group D

6. Free of all combustible material.

7. Prevent exposure to sunlight.

8. Posted signs “Organic PeroxideStorage” and “No Smoking”.

9. For controlled temperatureperoxides, emergency back uprefrigeration should be installed.

10. For controlled temperature per-oxides, emergency sources ofdry ice should be locally available.

Large quantities of organic peroxidesshould ideally be stored in speciallydesigned buildings of non-combustible construction.Detached buildings are the mostcommon and preferred facilities forstoring large quantities. Three basic

types of buildings are used depend-ing on the storage requirement ofthe peroxide and the amount thatwill be stored, plus local fire codes,insurance regulations and other laws.

A.Uncontrolled TemperatureStorage

Products stored in this type ofbuilding do not normally requirestorage temperatures outside ofthe normal ambient range (100˚Fmax.) to maintain assay, preventself accelerating decompositionand freezing. Uncontrolledtemperature storage howevershould not exceed 100˚F.Depending on climate, buildingscan be insulated, ventilated and/ordouble walled. (See Figure 2)

B.Refrigerated Storage FacilitiesProducts stored in this type offacility require lower than normalambient temperatures to preserveassay and to prevent self acceler-ating decomposition, e.g. chesttype freezers.

C.Walk In Refrigerated StorageBuildingThis type of facility is suitable forstoring large quantities of perox-ide which require refrigeratedconditions, e.g. Peroxydicarbo-nates. (See Figure 3)

STORAGE5

Figure 2

9

Door

Air OutAir

In

Air In

Plywood

Plywo

od

Corrugated Alum. Roofing

Sun Shield on East, South & West Surfaces

Corru

gate

d Alum

.

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 andaudio). 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 resistantdesign. 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 betweenrows of cartons; for air circulation.

STORAGE5

Figure 3 Walk-In Type Storage Unit

Refrigerated storage building and key requirements, inside and out.

Refrigerated Storage Building

ORGANIC PEROXIDE

10

SPILLAGE AND DISPOSAL6

Organic peroxide spills must betaken care of immediately. Spillscan normally be handled by spread-ing an inert absorbent materialdirectly on the spill, sweeping thearea and placing the sweepings inpolyethylene bags for disposal. Thesweepings should be wetted downwith water and disposed of immedi-ately by an approved disposalmethod (see below). When all thematerial has been picked up, washdown the spill area with surfactantand water to remove any traces ofperoxide. Allow for sufficient ventila-tion to aid in the removal of fumesthat may be present.

The following is the recommendedmethod for disposal of organicperoxides.

DILUTION AND INCINERATIONDue to current environmental regula-tions, this method is quickly becomingthe most preferred for liquid peroxidedisposal. Dilution of peroxide to no

more than 1% active oxygen, or nomore than 10% by weight (whicheveris lower) in a satisfactory solvent is recommended. Fuel Oil #2 ornon-flammable-polymerizablehydrocarbons (which are readilysoluble with the peroxide) are themost widely used solvents. Inciner-ation can be accomplished aftersatisfactory mixing. Incineration hasthe advantage of providing rapidand complete decomposition alongwith the elimination of decomposi-tion products. This method is notgenerally recommended for disposalof solid peroxides due to limitedsolubility of solid peroxides withhydrocarbons.

Incineration must be performed inaccordance with all applicableFederal, State and Local regulations.In general, an outside disposalcompany is used to perform this service.

11

PACKAGING7 TRANSPORTATION8

The containers in which organicperoxides are packaged include poly-ethylene bottles and jars, polyethylenelined bags and fiber drums andspecially coated steel drums.

Polyethylene is the preferred materialsince it is relatively inert and is flexibleenough to withstand normal pressurebuildup. Examples of typical containersare shown below.

Transportation regulations for organicperoxide formulations are located in the Code of Federal Regulations (CFR); 49 CFR 173.225.

Certain peroxides require refrigeratedtransportation as specified in 49 CFR173.21(f)(3).

FIRST AID9

Care should be exercised by allpersonnel handling organic peroxides.Acute hazards of organic peroxidesmay include skin/eye irritation, skin/eye corrositivity, and skin sensitization. Refer to MSDS or labelfor specific product health effects andfirst aid information.

For immediate medical assistancecontact the Rocky Mountain PoisonControl Center at 303-623-5716.

12

The following check list is provided asa summary in an attempt to avoidproblems in the storage, handling oruse of organic peroxides. The list is abasic safety and information guide, asit pertains to all organic peroxides.

1. Different classes of organic perox-ides have their own particularcharacteristics, specifications andhandling requirements. These areidentified on the product labels anddescribed in the appropriate productbulletins and MSDS. The productlabel is designed to indicate recom-mended storage temperature, specificproduct hazard characteristics, specialhandling information and appropriatefirst aid instructions. Product bulletinsprovide chemical composition data,sales specifications (including shelf life),physical properties, and safety infor-mation, such as storage temperatureand SADT (Tables 2 and 3).

2. One of the most important factorsto observe when working with anorganic peroxide is the recommendedstorage temperature. Exposure to atemperature that can lead to an acceler-ated decomposition may result in thegeneration of flammable gasses, and insome cases spontaneous ignition.

3. Refer to NFPA 432 for storageguidelines. Proper storage is critical tothe safe handling of organic peroxides,both those normally stored at ambienttemperatures and those requiringcontrolled temperature storage.Ventilation is important because aircirculation around peroxides stored atlow temperatures reduces the chanceof localized hot spots that could causedecomposition.

4. Storage areas for peroxides shouldhave explosion proof electrical equip-ment.

5. Organic peroxide inventoriesshould be rotated to avoid shelf lifeproblems.

6. Any observable gassing or distor-tion of the container, should be treatedvery carefully. Visible gassing of

organic peroxide containers may be anindication of imminent, possibly violentdecomposition.

7. Only minimal quantities of perox-ides should be kept in the immediateprocessing area.

8. Avoid contact with incompatiblematerials, such as oxidizers, reducingagents, promoters, acids or bases.

9. The safe use of organic peroxidesdemands that good housekeepingprocedures be meticulously practiced.

10. Heat, flame, contamination, shock,friction and static electricity are poten-tial hazards when an organic peroxideis being charged to a reaction. Careshould be taken to eliminate or mini-mize all of these.

11. Contamination can be avoided byusing proper equipment and propermaterials of construction. Polymericmaterials that may be soluble inorganic peroxide solutions should notbe used as reaction vessels.Compatible materials of constructioninclude stainless steel 304 or 316(preferred), HDPE, polytetrafluorothy-lene and glass linings. Do not usecopper, brass or iron.

12. Foreign materials, such as iron ordirt, should be avoided when chargingperoxides.

13. Pumps used for organic peroxidesmust be “dedicated use” to avoidpotential contamination.

14. Static buildup can be minimized byproper grounding and by keeping freefall distances to a minimum, especiallywhen working with static sensitiveinitiators, such as dry benzoyl perox-ide, and di-t-butyl peroxide.

15. Friction caused by pumpingincreases the temperature of thepumped solutions. Extra care shouldbe exercised when peroxide solutionsare being re-circulated to avoidtemperatures above SADT.

16. When peroxide samples are usedin analytical work, care should be exer-

cised to avoid any contamination.Clean, dry plastic or glass containersshould be used to transfer peroxidesamples. Dry ice should be availableto cool samples in an emergency.Direct heat should never be applied toorganic peroxides.

17. As a rule, dilution of pure peroxideswith compatible solvents will increasethe safety characteristics of the perox-ides.

18. Any spilled organic peroxidesshould be attended to immediately.Spills can normally be handled byspreading an inert absorbentsubstance directly on the spill, wettingwith water, sweeping the area andthen placing the sweepings in polyeth-ylene bags for appropriate disposal.

19. Where spills occur, allow for suffi-cient ventilation to aid in the removal offumes that may be present.

20. In disposing of organic peroxides,or the absorbent material that hasbeen used to remove spills, extremecare should be exercised. The wettedabsorbent material should be placed ina plastic bag and then incinerated.Federal, State and Local laws andenvironmental regulations must beobserved in choosing a disposalmethod.

21. The procedure for disposal ofempty peroxide containers mustinclude a thorough draining andshould include rinsing with water ora compatible solvent in particular forrefrigerated products. In accor-dance with Federal, State and localregulation, these can then be sentto an approved disposal site orincineration site.

22. Drum containers must always bethoroughly flushed and drained beforebeing sent to a reconditioner.

23. Cutting torches should never be used on empty peroxide drums.Flammable vapors may be present.

SAFETY CHECK LIST10

13

A thorough understanding of thesafety characteristics of organicperoxides is necessary in order toprevent accidents and to permit safeoperations. The recommendationsmade in this Bulletin are presented asa service to aid in the safe handling,storage and disposal of organicperoxides. The safety tests describedherein were used to establish safehandling procedures, packaging andshipping procedures for all organicperoxides. These guidelines aresuggested to aid users of organicperoxide initiators.

Available Safety Films

1. “Handle With Care”Discusses the hazards of peroxidesstorage and handling and offersrecommended procedures.

2. “Keep It Cool and Keep It Clean”Considers hazards and preventa-tive measures relative to MEKperoxide use in unsaturated polyester applications.

Other Information Sources

• National Fire Protection Association(NFPA) www.nfpa.org1-800-344-3555NFPA 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.org1-202-974-5200

Safety and Handling of OrganicPeroxides: A Guide (Publication#AS-109)

Responsible Care

Arkema Inc. is committed tothe ACC’s Responsible Care® andProduct Stewardship initiatives.

CONCLUSION11

14

VISIT US ON THE WEBwww.Arkema-Inc.com

SAFE USE AND HANDLING OF AMBIENT ORGANIC PEROXIDE INITIATORS12

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

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

© 2007 Arkema Inc. All rights reserved.IMPORTANT: 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 arisingfrom 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 anyprocess. The user should thoroughly test any application before commercialization. Nothing contained herein should be taken as an inducement to infringe any patent and the user

is advised to take appropriate steps to be assured that any proposed use of the product will not result in patent infringement.

®Luperox, Lupersol, are registered trademarks of Arkema Inc.

®Responsible Care is a registered trademark of the American Chemistry Council

Arkema Inc. is committed to the ACC’s Responsible Care andProduct Stewardship initiatives.

RESPONSIBLE CARE®

In Case of Emergency CallCHEMTREC at 1-800-424-9300

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