Document 48mjB1qRJjr7kEYXmQkokwvp

GLP COMPLIANT LABORATORIES Chilworth Technology the experts in process safety Chilworth Technology Ltd Beta House Southampton Science Park Southampton SO16 7NS UK Tel: 0722 Fax: 7866 Web: www.chilworth.co.uk Email: Mchilworth.co.uk Digital Documentation Chilworth Technology Limited. Registered Office as above. Registered in England and Wales. Number 2000153 Client F.A.O. Report Number Job Number Study Plan Number Sample Reference Honeywell Fluorine Products Europe BV Mr T Vink GLP15024BR1V1/06 J14388 GLP/15024/B S078106 Flammable and Explosive Properties of HFO-1234ze (trans-1,1,1,3-Tetrafluoropropene) Final Report 1 of 3 FOR AND ON BEHALF OF CHILWORTH TECHNOLOGY LIMITED 2006, Chilworth Technology Limited Report prepared by Christine Simmons Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV Page Number 2 of 20 C O N T E N T S PAGE NO. 1 COMPLIANCE WITH GOOD LABORATORY PRACTICE 3 2 REPORT AND TEST WORK APPROVAL STATEMENT 4 3 QUALITY ASSURANCE STATEMENT 5 4 INTRODUCTION 6 5 SUMMARY OF RESULTS 7 6 SAMPLE CHARACTERISATION 7 7 EC PHYSICO/CHEMICAL TEST A11, FLAMMABILITY (GASES) 8 8 COPY OF CHILWORTH TECHNOLOGY GLP CERTIFICATE 10 9 APPENDIX 1 11 9.1 Certificate of Analysis 11 10 APPENDIX 2 (NON-GLP TESTING) 12 11 CHEMICAL STRUCTURE, FORMULA AND BACKGROUND INFORMATION 13 12 ASSESSMENT OF OXIDISING PROPERTIES 14 12.1 Assessment of Oxidising Properties of HFO-1234ze 15 13 ASSESSMENT OF EXPLOSIVE PROPERTIES 16 13.1 Assessment of Explosive Properties of HFO-1234ze 17 14 CONCLUSIONS 18 Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV Page Number 6 of 20 4 INTRODUCTION This report contains the results of testing conducted on HFO-1234ze (trans-1,1,1,3Tetrafluoropropene) applying to GLP protocols and following guidelines stated in the relevant Chilworth Technology Limited Standard Operating Procedures. The following tests have been conducted: Flammability of Gases; EC Testing Method A11 (CTL Ref No. SOP 410) The test above has been conducted in accordance with the principles of GLP standards, whereas the following tests (which can be found in the appendix of this report) although carried out to the principle of GLP, are not claiming GLP compliance. Explosive Properties Analysis (EC Testing Method A14) (3 Parts) Part 1, Sensitivity to friction (calculation method) Part 2, Sensitivity to shock (calculation method) Part 3, Sensitivity to heating under confinement (calculation method) The signed study plan, raw data sheets, interim and final reports will be archived in designated filing cabinets in a locked archive room, for an indefinite period of time (minimum of 10 years). Access to the room will only be permitted by the GLP appointed archivist. Any computer generated data will be kept on labelled and numbered floppy discs and stored with the raw data, situated in the locked archive room. Any remaining sample will be stored in correctly labelled containers and placed in a locked sample storage room for a period of 1 month after the issue of the final report. Disposal of the sample will be by a registered waste disposal company and will fulfil all statutory and ecological regulations. This report together with any relevant graphs may also have been issued in digital format. In order to ensure that the integrity of the data is maintained, this signed hard copy will be considered to be the source document, and any digital versions will be considered to be copies. Name and address of sponsor: Honeywell Fluorine Products Europe BV Laarderhoogtweg 18 NL-1101 EA Amsterdam The Netherlands Name and address of sponsor contact: TNO Chemistry Utrechtseweg 48 PO Box 360 Zeist 3700 AJ Zeist The Netherlands Name and address of test facility: Chilworth Technology Limited Process Safety Laboratories Beta House Chilworth Science Park Southampton SO16 7NS United Kingdom Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV Page Number 7 of 20 5 SUMMARY OF RESULTS The following flammability of gases (A11) test result was obtained: Non-flammable The non-GLP Explosive and Oxidising Properties (A14) assessment concluded: The material will not possess oxidising or explosive properties The following are the key dates for the work reported here : Study Plan No. GLP/15024/B was approved on : Sample receipt date : Start date of the experimental work : Completion date of all the experimental work, including Non-GLP : 03/07/2006 10/07/2006 14/07/2006 17/07/2006 6 SAMPLE CHARACTERISATION Product Name : Batch No. : Use : Special Hazards : Appearance : HFO-1234ze (trans-1,1,1,3-Tetrafluoropropene) 40793-15-1 For research and development. Not fully investigated therefore all necessary precautions taken. Sample observed to be a gas. Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV Page Number 8 of 20 7 EC PHYSICO/CHEMICAL TEST A11, FLAMMABILITY (GASES) Test Objective and Information This method allows a determination of whether gases mixed with air at room temperature (circa 20C) and atmospheric pressure are flammable and, if so, over what range of concentrations. Mixtures of increasing concentrations of the test gas with air are exposed to an electrical spark and it is observed whether ignition occurs. The range of flammability is the range of concentration between the lower and the upper explosion limits. The lower and the upper explosion limits are those limits of concentration of the flammable gas in a mixture with air at which propagation of a flame does not occur. The test vessel is an upright glass cylinder having a minimum inner diameter of 50 mm and a minimum height of 300 mm. The ignition electrodes are separated by a distance of 3 to 5 mm and are placed 60 mm above the bottom of the cylinder. The cylinder is fitted with a pressure release opening. The apparatus is shielded to restrict explosion damage. A standing induction spark of 0.5 sec. duration, which is generated from a high voltage transformer with an output voltage of 10 to 15 kV (maximum of power input 300 W), is used as the ignition source. Using proportioning pumps, a known concentration of gas in air is introduced into the glass cylinder. A spark is passed through the mixture and it is observed whether or not a flame detaches itself from the ignition source and propagates independently. The gas concentration is generally, varied in steps of 1 - 2 % vol., until ignition occurs. The test standard is conducted according to EC Testing Method A11, performed to the ECs Classification, Packaging & Labelling of Dangerous Substances in the European Union Part 2, Testing Methods, Jan97. Directive 92/69/EC (Annex V to Directive 67/548/EC). Test Results for HFO-1234ze (trans-1,1,1,3-Tetrafluoropropene) Date : Operator : Temperature : SOP Reference : Apparatus : 17/07/2006 A. Jennings / P. Bremble 26C CTL SOP 410 FGT 1 Result : Non-flammable gas The table of results can be found on the next page. Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV Page Number 9 of 20 Table 7.1 : Full test results Spark Energy (mJ) C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A C/A Gas Concentration (%w/w) 1.6 2.0 3.0 4.0 10.0 12.0 15.0 20.0 25.0 30.0 35.0 21.0 17.0 19.0 18.0 23.0 27.0 6.0 8.0 9.0 11.0 13.0 14.0 16.0 Number of tests 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Ignition ? y (yes) / n (no) n n n n n n n n n n n n n n n n n n n n n n n n Comments Small blue glow Small blue glow Small blue glow Small blue glow Small orange glow Small orange glow & soot Small orange glow & soot Small blue glow Small blue glow Small blue glow Small blue glow Small blue / orange glow Small orange glow - C/A = Constant (high energy) Arc from 10 kV transformer. The apparatus and procedure were proven prior to testing by testing propane. In this test, a lower limit of flammability of 1.0 - 1.6% v/v and an upper flammable limit of 10 - 11.6 % were obtained. Comment With the test sample, ignition was obtained at an electrode gap of ca. 8 mm. However, as this is beyond the electrode gap stipulated in the standard, this result cannot be considered for classification of the material. However, this facet should be borne in mind when applying the data. Report Number GLP15024BR1V1/06 for Honeywell Fluorine Products Europe BV 8 COPY OF CHILWORTH TECHNOLOGY GLP CERTIFICATE Page Number 10 of 20 Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 11 of 20 9 APPENDIX 1 9.1 Certificate of Analysis Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 12 of 20 10 APPENDIX 2 (NON-GLP TESTING) The testing continued in the following pages, although carried out to the principle of GLP, are not claiming GLP compliance. Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 13 of 20 11 CHEMICAL STRUCTURE, FORMULA AND BACKGROUND INFORMATION INTRODUCTION An assessment of the potential oxidising and explosive properties of the material HFO1234ze has been conducted by Chilworth Technology for TNO Chemistry. The work has been undertaken (in response to Chilworth Technology quotation 15024/406/DJB/OH7-P/T) to identify whether the material could exhibit oxidising and/or explosive properties. As the material exists in the gas phase at room temperature, it is not possible to carry out formal testing for oxidising or explosive properties (EC tests A17 and A14, respectively), and therefore an assessment is undertaken. Name : Synonyms : Formula : Molecular weight : EC Number : CAS Number : Physical State : Chemical Structure : trans-1,1,1,3-tetrafluoropropene HFO1234ze C3H2F4 114.05 g.mol-1 Not listed 1645-83-6 Gas F CF H F C CF H Source of information : Manufacturer : Honeywell Fluorine Products Europe BV Honeywell Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 14 of 20 12 ASSESSMENT OF OXIDISING PROPERTIES Experimental techniques are available for the classification of a substance or preparation as oxidising. These are described in EC Test A17. However, Test A17 need not to be carried out when examination of the structural formula establishes beyond reasonable doubt that the substance has no oxidizing properties. The supplement to the A17 method describes situations in which experimental assessment of oxidising properties is not necessary. The contents of this supplement are outlined below. Compounds which have no highly electronegative atom - oxygen, fluorine, chlorine, bromine - are not likely to possess oxidizing properties. Similarly, where these elements are present but the atoms are only bonded to carbon and/or hydrogen, then oxidizing properties are unlikely. A substance may have oxidizing properties when: the electronegative atoms which are present constitute a high proportion of the molecule and are bound to elements in a high oxidation state; the electronegative atoms are bonded to each other or to other electronegative elements such as iodine, nitrogen, sulphur or phosphorus. As the ability to predict the reactivity of chemicals compounds from their structure is still limited, the best approach is by analogy with existing compounds. Table 2 provides a list of oxidizing compounds and reactive groups which increase the oxidizing power. However, this list is not exhaustive. If the substance meets one of the above criteria, the lack of any reactive group named in Annex 1 may not be sufficient to justify not performing the A 17 test. For organic substances only, the oxygen balance (OB) calculation may be useful as a criteria combined with an examination of the chemical structure as a means of predicting oxidizing properties. For an organic substance (CXHYOZ) of molecular weight M, the OB is calculated as follows: Oxygen balance = -1600(2X + Y/2 -Z) / mol. wt. Although experts think that the OB calculation is a possible approach, there is currently no consensus on the criteria that should be used. For the moment, professional judgment will be required to use the OB value on a case by case basis. In any case, if theoretical considerations are used to exclude performance of the test A 17, the reasons and all relevant information should be clearly stated in the technical dossier. Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 15 of 20 12.1 Assessment of Oxidising Properties of HFO-1234ze Examining the structure of HFO-1234ze, the following observations can be made: The molecule does not contain any functional groups listed in Table 2. Although this list is not exhaustive, this is a significant observation as most commonly occurring oxidising functional groups are contained within the list. According to the two criteria quoted, oxidising properties can exist when: o the electronegative atoms which are present constitute a high proportion of the molecule and are bound to elements in a high oxidation state The HFO-1234ze molecule has a high proportion of electronegative atoms (4 fluorine atoms out of an overall atom count of 9). However, these four electronegative atoms are not bound to elements in high oxidation states. All of the fluorine atoms are bound to carbons only. o the electronegative atoms are bonded to each other or to other electronegative elements such as iodine, nitrogen, sulphur or phosphorus. In the case of HFO-1234ze, the electronegative atoms are not bound to one another, nor to any other electronegative elements. o Assessment against these two criteria indicates strongly that the molecule will not have oxidising properties. In every respect of the oxidising solids exemption procedure, HFO-1234ze (trans-1,1,1,3tetrafluoropropene) does not show any evidence of possessing oxidising properties. On the basis of this exercise, the material should be considered as not oxidising. The material meets all criteria for exemption from testing and has a structure not at all conducive with that required to exhibit oxidising tendencies. Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 16 of 20 13 ASSESSMENT OF EXPLOSIVE PROPERTIES Experimental techniques are available for the classification of a substance or preparation as explosive. These are described in EC Test A14. However, according to the OECD testing methods publication, test A14 need not to be carried out when examination of the structural formula establishes beyond reasonable doubt that the substance has no explosive properties (ie. it is not capable of rapid gas or heat release). The UN Transport of Dangerous Goods, Manual of Tests and Criteria1 which is referred to in the OECD testing publication presents a reasonably comprehensive procedure through which exemption can be assessed (Appendix 6 Screening procedures). The following extracts are taken from this UN publication: Explosive properties are associated with the presence of certain chemical groups in a molecule which can react to produce very rapid increases in temperature or pressure. The screening procedure is aimed at identifying the presence of such reactive groups and the potential for energy release. Explosives testing need not be applied where: (a) when there are no chemical groups associated with explosive properties present in the molecule. Examples of explosive groups are given in Table 2. (b) when the substance contains chemical groups associated with explosive properties which include oxygen and the calculated oxygen balance is less than -200 (see Section 3 for calculation equation) (c) When the organic substance or a homogeneous mixture of organic substances contain chemical groups associated with explosive properties but the exothermic decomposition energy is less than 500 J/g and the onset of exothermic decomposition is below 500C. The exothermic decomposition energy may be determined using a suitable calorimetric technique. Table 2 : Examples of Functional Groups Indicating Explosive Properties in Organic Materials Structural Feature C-C unsaturation C-Metal, N-metal Contiguous nitrogen atoms Contiguous oxygen atoms N-O N-Halogen O-Halogen Examples Acetylenes, acetylides, 1,2-dienes Grignard reagents, organolithium compounds Azides, aliphatic azo compounds, diazonium salts, hydrazines, sulphonylhydrazides Peroxides, ozonides Hydroxylamines, nitrates, nitro compounds, nitroso compounds, N-oxides, 1,2-oxazoles Chloramines, fluoramines Chlorates, perchlorates, iodosyl compounds 1 Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, 4th revised edition, UN (New York and Geneva), 2003, ISBN 92-1-139087-7. Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 17 of 20 13.1 Assessment of Explosive Properties of HFO-1234ze Examination of the structural formula of HFO-1234ze indicates: The presence of an unsaturated ethylene group (-C=C-) in the molecule, which is associated with energetic behaviour and in rare occasions, explosive properties (Table 2). The ethylene group is present in a high concentration relative to the molecular weight of the molecule. The bond energy5 of the C=C bond is 70 kJ.mol-1, the projected reaction energy of the molecule is therefore 613.8 J.g-1. This suggests that the material could pose a potential explosivity problem, as the energy released on decomposition or polymerisation could be >500 J.g-1. There is a risk associated with the polymerisation of unsaturated fluoromonomers such as HFO-1234ze (trans-1,1,1,3-tetrafluoropropene). A comparison can be made to the analogous compound trifluoroethylene F2C=CHF (CAS number 359-11-5). At pressures above 14 bar, and possibly below, trifluoroethylene deflagrates with tenfold pressure rises, when initiated by an exploding wire. The tests were carried out on air-free and inhibited commercial material2. Compounds containing similar functional groups to those in HFO-1234ze, such as ethylene and tetrafluoroethylene exhibit energetic properties. Explosive reaction of ethylene occurred in the absence of air at 350C, under 17 bar of pressure3. Tetrafluoroethylene is inhibited with a terpene inhibitor to prevent spontaneous polymerisation, in its absence, the monomer will spontaneously explode if ignited4. However, both ethylene and tetrafluoroethylene, are classified as flammable and are not classified as explosives - even though the energy release potential of ethylene is 2500 J.g-1 and tetrafluoroethylene is 700 J.g-1. References to explosive properties when associated with these materials generally refer to flammability or rapid polymerisation potential rather than detonation capability. Examination of compounds with similar structural properties and numbers of atoms to that of HFO-1234ze, demonstrates that fluoromonomers such as these are not classified as explosives. Materials such as 3,3,3-Trifluoropropene with an energy release potential of 729 J.g-1, and 2-Bromo-3,3,3-trifluoropropene are classified as flammable, but are not classified as explosives. A CHETAH evaluation of the energy release potential of HFO-1234ze has been conducted (Table 4). The analysis indicates that the overall energy release potential of the compound is LOW. It can be concluded that, on the basis of the factors above and on the balance of data available, the material will not exhibit explosive properties. Although the presence of the unsaturated ethylene (-C=C-) group indicates the possibility that the material may exhibit explosive properties, as a result of the risk associated with the polymerisation of unsaturated fluoromonomers, by comparison of HFO-1234ze to classified analogous compounds it can be concluded that no explosive properties should be exhibited by the substance. 2 Hulbert, J. D. et al., Chem. Eng. News 1997, 75(51), 6. 3 Waterman, H. I. et al., J. Inst. Petr. Tech., 1931, 17, 505. 4 Graham, D. P., J. Org. Chem., 1966, 31, 956. 5 Grewer, T in Thermal Hazards of Chemical Reactions, Industrial safety series, volume 4 Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 18 of 20 14 CONCLUSIONS An examination of the structural formula of HFO-1234ze (trans-1,1,1,3-tetrafluoropropene) has been conducted, along with other thermodynamic calculations, to assess the likelihood of the material exhibiting oxidising or explosive properties. It has been concluded, beyond reasonable doubt, that the material will not possess oxidising or explosive properties. The majority of the data for exemption has been provided by analogy with similar fluorinated, unsaturated alkenes. Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 19 of 20 Table 3: Functional Groups Imparting Oxidising Properties Organic Nitro compounds N-Halogen Compounds (N-X) Oxohalogen Compounds Interhalogen Compounds Nitrates (salts or esters) Nitrites (salts or esters) Nitroalkyl Nitroaryl Fluorodinitro Metal oxides Metal oxometallates N-Haloimides Difluoroamino Difluoroaminopolynitroaryl Acyl hypohalites Hypofluorites Bis(fluoroxy)perhaloalkanes Perchlorates Chlorates Chlorites Hypochlorites Perbromates Bromates Bromites Hypobromites Periodates Iodates Difluoroperchloryl salts Dioxygenyl polyfluorosalts NO3- M+ NO2- M+ NO2-R NO2-Ar F(NO2)2-CMOn M+ MOn-C(O)-NX-C(O)- NF2 (NO2)n-Ar-NF2 RC(O)-OX FOF3CCI(OF)2 etc CIO4CIO3CIO2CIOBRO4BrO3BrO2BrOIO4IO3F2CIO2+ ZO2+ [MFn]- or 02+ EFn]- Metal polyhalohalogenates M+ [XX'n]- O2N-O-R ON-O-R Non-GLP Report Number GLP15024/B for Honeywell Fluorine Products Europe BV Page Number 20 of 20 Table 4: CHETAH Evaluation Results for HFO-1234ze 12/07/2006 ASTM PROGRAM CHETAH 7.3 COMMITTEE E-27 CHEMICAL THERMODYNAMIC AND ENERGY APPRAISAL PROGRAM ENERGY RELEASE EVALUATION Title : HFO-1234ze Compound Name : Molecule 1 Formula : C3H2F4 Molecular Weight : 114.043 Amount : 1 Gram(s) Heat of Formation at 25 C : -189.770 kcal/mol Hazard Classification Section: Primary Results: Criterion Maximum heat of decomposition (#2) Over-all Energy Release Potential Net Plosive Density(#4) Value -0.450 0.330 Cannot be Units kcal/g determined Hazard Classification(#1) MEDIUM LOW Secondary Results: The following criteria are parameters of the over-all ERE calculation and serve to enhance the fit for particular classes of compounds, but are not generally useful for hazard analysis out of context: Criterion Fuel Value - Heat of Decomposition Oxygen Balance(#3) CHETAH ERE Criterion 4 Total Number of Peroxide Bonds Value -1.496 -84.176 25.670 0.000 Units kcal/g g O2/100g kcal^2/gmole.gm Hazard Classification(#1) MEDIUM HIGH LOW Warning: Notes: #1 #2 #3 #4 These ratings only apply to hazards associated with strong shock.This does not imply the absence of other hazards. This evaluation was developed to classify a composition as able or not able to decompose with violence, if subjected to the proper conditions. Information on the interpretation of the hazard classification criteria used by CHETAH may be found in the CHETAH documentation (ASTM publication DS-51A) and in the User's Manual. For decomposition products shown. Experience has shown that the oxygen balance criterion is useful only for compounds composed of the elements C, H, N, and O.It was derived for explosives, especially nitrates [W.C.Lothrop and G.R Handrick, Chem.Rev.1949,44,419-45],for example it is not valid for water. Units are grams additional O2 per 100g reactants needed for complete combustion. Sum of auxoplosive and plosophoric weights per gram of mixture.(J. Chem. Ed. v66, A137 (1989) Decomposition Products (chosen to maximize heat of decomposition): Moles State Species 2.500 ref-cr C Carbon 0.500 gas CF4 Carbontetrafluoride 2.000 gas FH Hydrogen fluoride Heat of Combustion Section Fuel Value (Net Heat of Combustion): Mass Basis Mole Basis -1.946 kcal/g -221.980 kcal/mol -8.144 kJ/g -928.765 kJ/mol -3503.642 Btu/lb Combustion Products (Chosen for Fuel Value and Net Heat of Combustion): Moles State Species 3.000 gas CO2 Carbondioxide 2.000 gas FH Hydrogen fluoride 1.000 ref-gas F2 Fluorine Groups Present in this Compound:Description CF3-(C) Count 1 1