t-butyl hydroperoxide 70 Water IV III 55 gal t-butyl peroxy-2-ethylhexanoate 97 II 55 gal

Transcription

1 NFPA Hazardous Materials Code TIA Log No Reference: Tables F.2.3, F.3.3, F.4.3, F.5.3, and F.6.3 Comment Closing Date: September 14, 2012 Submitter: Henry L. Febo, Jr., FM Global 1. Revise Tables F.2.3, F.3.3, F.4.3, F.5.3, and F.6.3 according to Table F.1 (Typical Organic Peroxide Formulations). These changes need to be made based upon information contained in Table F.1. Table F.1 lists all organic s by name and the other tables list them by Class I through V on respective tables. Modifications consist of changing the Class for 28 listings and deleting one listing, a product in a container size no longer permitted for transport. The changes to Class are shown in the attached table which includes several additional columns from the current F.1 for identification purposes. Unlisted columns in the current table are unchanged. Table of Organic Peroxides (Annex F-1) Changes Organic Peroxide Concentration Diluent Current Class New Class Container t-amyl peroxy III II 55 gal t-amyl 75 OMS III II 5 gal t-amyl peroxypivalate 75 OMS III II 5 gal cumyl 95 - IV III 55 gal hydro 70 DTBP and t- II I 55 gal BuOH hydro 70 Water IV III 55 gal peroxy III II 5 gal peroxy-2-97 II 55 gal DELETE THIS LISTING peroxy-2-50 DOP or OMS IV III 5 gal peroxy 2-ethylhexyl 95 - III II 5 gal peroxyiso 75 OMS II I 5 gal 75 OMS III II 5 gal peroxypivalate 45 OMS IV III 5 gal Cumyl 75 OMS III II 5 gal Cumyl peroxyneoheptanoate 75 OMS III II 5 gal 1,1-Di(t-amylperoxy) cyclohexane 80 OMS or BBP III II 5 gal Di (4-t-butylcyclohexyl) 98 - III II 88 lb Di-t-butyl 99 - III II 55 gal Di-sec-butyl 98 - II I 1 gal 1,1-Di(t-butylperoxy)-3,3, II I 5 gal trimethyl-cyclohexane Didecanoyl 98 - III II 50 lb Dilauroyl 98 - IV III 110 lb 2,5-Dimethyl-2, II I 4@5 lb di(benzoylperoxy)hexane 2,5-Dimethyl-2,5-di(tbutylperoxy)hexane 92 - III II 30 gal 2,5-Dimethyl-2,5-di( III II 5 gal ethylhexanoylperoxy)hexane Ethyl-3,3-di(t-amylperoxy) 75 OMS III II 5 gal Ethyl-3,3-di(t-butylperoxy) 75 OMS III II 5 gal p-menthyl hydro 54 Alcohols and IV III 55 gal ketones 2.4-Pentanedione 4.0% AO Water and solvent IV III 5 gal

2 Organic Peroxide Concentration Diluent Table F.1 Typical Organic Peroxide Formulations Control Emergency Hazard Identification 2 F C F C Health Flammability Reactivity Class Container t-amyl hydro 88 Water III 55 gal (208 L) t-amyl peroxyacetate 60 OMS III 5 gal (19 L) t-amyl peroxybenzoate II 5 gal (19 L) t-amyl peroxy II 55 gal (208 L) t-amyl 75 OMS II 5 gal (19 L) t-amyl peroxypivalate 75 OMS II 5 gal (19 L) cumyl IV III 55 gal (208 L) n-butyl-4,4-di(t-butyl II 5 gal (19 L) peroxy) valerate hydro 90 Water and t- BuOH I 5 gal (19 L) hydro 3 70 DTBP and t-buoh II 55 gal (208 L) hydro 3 70 Water IV III 55 gal (208 L) monoperoxymaleate I 1 lb 0.5 kg) peroxyacetate 75 OMS I 5 gal (19 L) peroxyacetate 60 OMS I 5 gal (19 L) peroxybenzoate II 5 gal (19 L) peroxy III 5 gal (19 L) peroxy II 55 gal (208 L) peroxy-2- peroxy-2-50 DOP or OMS 50 DOP or OMS IV III 5 gal (19 L) III 55 gal (208 L) peroxy III 5 gal (19 L) ethylhexyl 75 OMS II 5 gal (19 L) peroxyiso peroxy isopropyl 92 OMS I 5 gal (19 L) peroxy isopropyl 75 OMS II 5 gal (19 L) 75 OMS III 5 gal (19 L) peroxypivalate 75 OMS II 5 gal (19 L) peroxypivalate 45 OMS IV III 5 gal (19 L) Cumyl hydro 88 Cumene III 55 gal (208 L) Cumyl 75 OMS III 5 gal (19 L) Cumyl peroxyneoheptanoate 75 OMS III 5 gal (19 L)

3 Organic Peroxide Concentration Diluent Table F.1 Typical Organic Peroxide Formulations (continued) Control Emergency Hazard Identification 2 F C F C Health Flammability Reactivity Class Container Diacetyl 25 DMP II 5 gal (19 L) 1,1-Di(t-amylperoxy) cyclohexane 80 OMS or BBP III 5 gal (19 L) I 1 lb (0.5 kg) 78 Water II 25 lb (11 kg) 75 Water III 25 lb (11 kg) 70 Water IV 25 lb (11 kg) 55 Plasticizer T III 350 lb (160 kg) (slurry) (slurry) (powder) (powder) Di (4-t-butylcyclohexyl) 55 Plasticizer and water T IV 350 lb (160 kg) 50 Plasticizer T III 380 lb (170 kg) 50 Plasticizer and water 40 Water and plasticizer T IV 380 lb (170 kg) T IV 380 lb (170 kg) 40 Water IV 5 gal (19 L) 35 Dicalcium phosphate dihydrate or calcium sulfate dihydrate V 100 lb (45 kg) 35 Starch IV 100 lb (45 kg) III 88 lb (40 kg) Di-t-butyl III 55 gal (208 L) 2,2-Di(t-butylperoxy) 50 Toluene I 1 gal (4 L) butane 1,1-Di(t-butylperoxy) cyclohexane Di-sec-butyl Di-sec-butyl Di(2-t-butylperoxyisopropyl) benzene Di(2-tbutylperoxyisopropyl) benzene Di(butylperoxy) phthalate 1,1-Di(t-butylperoxy)- 3,3,5-trimethylcyclohexane 1,1-Di(t-butylperoxy) -3,3,5-trimethylcyclohexane 80 OMS or BBP II 5 gal (19 L) II 1 gal (4 L) 75 OMS II 5 gal (19 L) III 100 lb (45 kg) 40 Clay V 100 lb (45 kg) 40 DBP IV 30 gal (110 L) II 5 gal (19 L) 40 Calcium V 100 lb (45 kg)

4 Organic Peroxide Concentration Diluent Dicetyl Table F.1 Typical Organic Peroxide Formulations (continued) Control Emergency Hazard Identification 2 F C F C Health Flammability Reactivity Class Container IV 44 lb (20 kg) Dicumyl IV 55 gal (208 L) Dicumyl 40 Clay or calcium V 100 lb (45 kg) Didecanoyl III 50 lb (23 kg) Di-2,4-dichlorobenzoyl Di(2-ethylhexyl) Di(2-ethylhexyl) 50 DBP and silicone T III 5 gal (19 L) II 1 gal (4 L) 40 OMS IV 5 gal (19 L) Diisopropyl I 10 lb (4.5 kg) Diisopropyl 30 Toluene III 5 lb (2.3 kg) Di-n-propyl I 1 gal (4 L) Di-n-propyl 85 OMS I 1 gal (4 L) Dilauroyl IV III 110 lb (50 kg) 2,5-Dimethyl-2,5-di (benzoylperoxy)hexane 2,5-Dimethyl-2,5-di (t-butylperoxy)hexane 2,5-Dimethyl-2,5-di (tbutylperoxy)hexane 2,5-Dimethyl-2,5-di (2- ethylhexanoylperoxy) hexane 2,5-Dimethyl-2,5- dihydroperoxyhexane Ethyl-3,3-di(tamylperoxy) Ethyl-3,3-di(tbutylperoxy) Ethyl-3,3-di(tbutylperoxy) p-menthyl hydro II 5 lb 2.3 kg) III 30 gal (110 L) 47 Calcium or silica V 100 lb (45 kg) III 5 gal (19 L) 70 Water II 100 lb (45 kg) 75 OMS III 5 gal (19 L) 75 OMS III 5 gal (19 L) 40 Clay or calcium silicate 54 Alcohols and ketones V 100 lb (45 kg) T IV III 55 gal (208 L) 9.0% AO DMP III 5 gal (19 L) 5.5% AO DMP IV 5 gal (19 L) 9.0% AO Water and glycols IV 5 gal (19 L)

5 Organic Peroxide Concentration Diluent and Cyclohexanone mixture 2,4-Pentanedione Peroxyacetic acid, Type E, stabilized Table F.1 Typical Organic Peroxide Formulations (continued) Control Emergency Hazard Identification 2 F C F C Health Flammability Reactivity Class Container 9.0% AO DMP III 5 gal (19 L) 4.0% AO Water and solvent 43 Water, HOAc, and H 2 O IV III 5 gal (19 L) II 30 gal (110 L) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. 3 See NFPA 30, Flammable and Combustible Liquids Code, for additional storage requirements. 4 T Temperature control should be considered to reduce fire hazard depending on packaging size and recommendations in manufacturers literature. Note: Diluents: AO Active oxygen; BBP Butyl benzyl phthalate; DBP Dibutyl phthalate; DMP Dimethyl phthalate; DOP Dioctyl phthalate; DTBP Di-tertiary-butyl ; HOAc Acetic acid; H 2 O 2 Hydrogen ; OMS Odorless mineral spirits; t-buoh Tertiary butanol.

6 Table F.2.3 Typical Class I Formulations hydro 90 Water & t- BuOH hydro 3 70 DTBP and t-buoh monoperoxymaleate gal (19 L) gal (208 L) lb 0.5 kg) peroxyacetate 75 OMS gal (19 L) peroxyacetate 60 OMS gal (19 L) 75 OMS gal (19 L) peroxyiso peroxy isopropyl 92 OMS gal (19 L) lb (0.5 kg) 2,2-Di(t-butylperoxy) 50 Toluene gal (4 L) butane Di-sec-butyl gal (4 L) 1,1-Di(t-butylperoxy)- 3,3,5-trimethylcyclohexane gal (19 L) Diisopropyl 2,5-Dimethyl-2,5- di(benzoylperoxy) hexane Di-n-propyl Di-n-propyl lb (4.5 kg) lb 2.3 kg) gal (4 L) 85 OMS gal (4 L) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. Note: Diluents: OMS Odorless mineral spirits; t-buoh Tertiary butanol.

7 Table F.3.3 Typical Class II Formulations t-amyl peroxybenzoate gal (19 L) t-amyl peroxy gal (208 L) t-amyl 75 OMS gal (19 L) t-amyl 75 OMS gal (19 L) peroxypivalate n-butyl-4,4-di(tbutylperoxy) gal (19 L) valerate 70 DTBP and gal (208 L) hydro 3 t-buoh gal (19 L) peroxybenzoate peroxy gal (19 L) peroxy gal (19 L) ethylhexyl peroxy gal (208 L) ethylhexyl peroxyiso 75 OMS gal (19 L) peroxy isopropyl 75 OMS gal (19 L) 75 OMS gal (19 L) peroxypivalate 75 OMS gal (19 L) Cumyl 75 OMS gal (19 L) Cumyl 75 OMS gal (19 L) peroxyneoheptanoate Diacetyl 25 DMP gal (19 L) 1,1-Di(t-amylperoxy) cyclohexane 80 OMS or BBP gal (19 L) 78 Water lb (11 kg) Di(4-tbutylcyclohexyl) lb (40 kg) Di-t-butyl gal (208 L) 1,1-Di(t-butylperoxy) cyclohexane Di sec-butyl Di-sec-butyl 80 OMS or BBP gal (19 L) gal (4 L) 75 OMS gal (19 L) Didecanoyl lb (23 kg) 1,1 Di(t-butylperoxy) trimethyl cyclohexane gal (19 L)

8 Table F.3.3 Typical Class II Formulations (continued) Di(2-ethylhexyl) 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane 2,5-Dimethyl-2,5-di- (2-ethyl hexanoylperoxy) hexane 2,5-Dimethyl-2,5- dihydroperoxy hexane 2,5-Dimethyl-2,5- dihydroperoxy hexane Ethyl-3,3-di (tamylperoxy) Ethyl-3,3-di (tbutylperoxy) gal (4 L) gal (110 L) gal (19 L) lb 2.3 kg) 70 Water lb (45 kg) 75 OMS gal (19 L) 75 OMS gal (19 L) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. Note: Diluents: BBP Butyl benzyl phthalate; DMP Dimethyl phthalate; DTBP Di-tertiary-butyl ; OMS Odorless mineral spirits; t-buoh Tertiary butanol.

9 Table F.4.3 Typical Class III Formulations t-amyl hydro 88 Water gal (208 L) t-amyl peroxyacetate 60 OMS gal (19 L) cumyl gal (208 L) hydro 70 Water gal (208 L) peroxy-2- t-amyl peroxy 2- t-amyl t-amyl peroxypivalate peroxy 2- peroxy-2-50 DOP or OMS gal (19 L) gal (208 L) 75 OMS gal (19 L) 75 OMS gal (19 L) gal (19 L) 50 DOP or OMS gal (208 L) 45 OMS gal (19 L) peroxypivalate peroxy gal (19 L) ethylhexyl 75 OMS gal (19 L) Cumyl hydro 88 Cumene gal (208 L) Cumyl 75 OMS gal (19 L) Cumyl 75 OMS gal (19 L) 1,1 Di(t-amylperoxy) 80 OMS or BBP gal (19 L) 75 Water lb (11 kg) 55 Plasticizer T lb (160 kg) 50 Plasticizer T lb (170 kg) Di(4 t- butylcyclohexyl) peroxygi lb (40 kg) Di t-butyl gal (208 L) Di(2-t-butylperoxyisopropyl) lb (45 kg) benzene Didecanoyl lb (23 kg) Di-2,4- dichlorobenzoyl 50 DBP and silicone T gal (19 L) Diisopropyl 30 Toluene lb (2.3 kg) Dilauroyl lb (50 kg) p-menthyl hydro 54 Alcohols and ketones T gal (208 L)

10 Table F.4.3 Typical Class III Formulations (continued) 2,5 Dimethyl 2,5 di (t-butylperoxy) hexane 2,5 Dimethyl 2,5 di (2 ethyl hexanoylperoxy) Ethyl 3,3 di (tamylperoxy) Ethyl 3,3 di (tbutylperoxy) and Cyclohexanone mixture 2,4-Pentanedione gal (110 L) gal (19 L) 75 OMS gal (19 L) 75 OMS gal (19 L) 9.0% AO DMP gal (19 L) 9.0% AO DMP gal (19 L) 4.0% AO Water and solvent gal (19 L) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. 3 Also a flammable liquid; see NFPA 30, Flammable and Combustible Liquids Code, for storage requirements. 4 T Temperature control should be considered to reduce fire hazard depending on packaging size and recommendations in manufacturers literature. Note: Diluents: AO Active oxygen; BBP Butyl benzyl phthalate; DBP Dibutyl phthalate; DMP Dimethyl phthalate; DOP Dioctyl phthalate; OMS Odorless mineral spirits.

11 Table F.5.3 Typical Class IV Formulations cumyl gal (208 L) hydro 70 Water gal (208 L) peroxy 2-50 DOP or OMS gal (19 L) peroxypivalate 45 OMS gal (19 L) 70 Water lb (11 kg) (slurry) (slurry) (powder) Di(t-butylperoxy) phthalate Dicetyl 55 Plasticizer and water 50 Plasticizer and water 40 Water and plasticizer T lb (160 kg) T lb (170 kg) T lb (170 kg) 40 Water gal (19 L) 35 Starch lb (45 kg) 40 DBP gal (110 L) lb (20 kg) Dicumyl gal (208 L) Di(2-ethylhexyl) 40 OMS gal (19 L) Dilauroyl lb (50 kg) P Menthyl hydro 2,4 Pentanedione 54 Alcohols and ketones T gal (208 L) 55% AO DMP gal (19 L) 9.0% AO Water and glycols 4.0% AO Water and solvent gal (19 L) gal (19 L) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. T Temperature control should be considered to reduce fire hazard depending on packaging size and recommendations in manufacturers literature. Note: Diluents: DBP Dibutyl phthalate; DMP Dimethyl phthalate; DOP Dioctyl phthalate; OMS Odorless mineral spirits; AO Active oxygen.

12 Table F.6.3 Typical Class V Formulations (powder) Di(2-tbutylperoxyisopropyl) benzene 1,1-Di(t-butylperoxy) -3,3,5- trimethylcyclohexane 35 Dicalcium phosphate dehydrate or calcium sulfate dihydrate lb (45 kg) 40 clay lb (45 kg) 40 Calcium Dicumyl 40 Clay or calcium 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane Ethyl-3,3-di (tbutylperoxy) 47 Calcium or silica 40 Clay or calcium silicate lb (45 kg) lb (45 kg) lb (45 kg) lb (45 kg) 1 These columns refer to temperatures in the Department of Transportation (DOT) Organic Peroxides Table. Refer to document 49 CFR for details. 2 The column refers to NFPA 704, Standard System for the Identification of the Hazards of Materials for Emergency Response, hazard ratings for health, flammability, and reactivity. See NFPA 704 for details. AO Active oxygen. Statement of problem: The current classification of the products being changed was found to be incorrect and non-conservative based on the latest testing and other information on these materials. The incorrect classifications results in inconsistent ranking when compared with listings by other international code organizations resulting in confusion for the users. Since all changes are in the direction of higher hazard, improvements on individual sites may be required to safely store the affected materials. Previously the storage classification for organic formulations was based upon consideration of incidents involving said formulations, along with expert opinion of technically oriented individuals from the NFPA committee. OPPSD now recommends a more objective and globally consistent method for such classification. The Dutch Code PG S8 (Organic s: Storage, Guideline for the labour-safe, environment safe and fire-safe storage of organic s, December 2011) and similar European classification systems are based on transport classification (United Nations Guideline) in addition to burning rate measured using either large or small scale burning tests. Submitter s Substantiation: The Organic Peroxide Producers Safety Division (OPPSD) of the Society of the Plastics Industry (SPI) offers comments related to NFPA 400 Hazardous Materials Code. These comments are specifically related to Chapter 14, Organic Peroxide Storage. They reflect the expert opinion of the OPPSD members: AkzoNobel, Arkema, LyondellBasell, Pergan, Syrgis and United Initiators. The OPPSD recently reviewed the current table of storage classifications for organic formulations found as Annex F: Typical Organic Peroxide Formulations in NFPA 400. The text of Chapter 14 of NFPA 400 allows classification to be made by parties with technical awareness of these formulations. Additionally Appendix A of NFPA 400 states: each organic formulation is to be classified with respect to quantity and type of container. Classification should be done by professionals familiar with the properties of the organic formulation. Property information used for classification of organic formulations for UN Transportation of Dangerous Goods can be useful for the NFPA 400 classification. Other useful information includes density, small fire test data and fire data for response to sprinkler conditions. As an association of manufacturers of organic s, the OPPSD meets this requirement. The storage classifications listed in the 2010 revision of NFPA 400 were reviewed in relation to a similar list of formulations found in European guidance documents as well as having knowledge of the data from which the classifications were developed. The new

13 listing criteria have been expanded to include tests to rate the burning characteristics in simulated storage configurations that had not been included in the original UN classification system. As a result of the review the OPPSD suggests changes to the storage classification and the recommendations are made after careful and thorough discussion amongst its members. This material was discussed by a small NFPA 400 Task Group that included two other committee members in addition to the submitters and two interested outside participants. They agreed that this material should be submitted as a TIA. Emergency Nature: The proposed TIA intends to correct a previously unknown existing hazard. Anyone may submit a comment by the closing date indicated above. To submit a comment, please identify the number of the TIA and forward to the Secretary, Standards Council, 1 Batterymarch Park, Quincy, MA