{"operation":"document","citation":"19-0077","title":"LANXESS Solutions, US, Inc. — Hazardous Materials Safety Interpretation","source_type":"guidance","agency":"Pipeline and Hazardous Materials Safety Administration","status":"guidance","official":true,"published_on":"2020-06-24","effective_on":null,"summary":"19-0077 response to LANXESS Solutions, US, Inc. concerning 171.22.","machine_formats":{"json":"https://regulus.evalyn.ai/document/phmsa-interpretation-19-0077.json","markdown":"https://regulus.evalyn.ai/document/phmsa-interpretation-19-0077.md"},"app_url":"https://regulus.evalyn.ai/document/phmsa-interpretation-19-0077","source_url":"https://www.phmsa.dot.gov/sites/phmsa.dot.gov/files/docs/standards-rulemaking/hazmat/interpretations/74116/190077.pdf","body":"<<<PAGE 1>>>\n\nU.S. Department\nof Transportation\nPipeline and Hazardous\nMaterials Safety\nAdministration\n1200 New Jersey Avenue, SE\nWashington, DC 20590\nJune 24, 2020\nErnest Marcel, CDGP, DGSA\nLANXESS Solutions, US, Inc.\nPTSE/PSRA Group\n2 Armstrong Road\nShelton, CT, 06484\nReference No. 19-0077\nDear Mr. Marcel:\nThis letter is in response to your June 10, 2019, email requesting clarification of the Hazardous\nMaterials Regulations (HMR; 49 CFR Parts 171-180) applicable to mixtures containing a\nhazardous material that is listed in the Hazardous Materials Table (HMT) with a “+” in Column\n(1) and assigned Special Provision (SP) 279 in the UN Model Regulations and the International\nMaritime Dangerous Goods (IMDG) Code. Specifically, you ask about the classification of a\nproduct containing less than 5% toluene diisocyanate.\nWe have paraphrased and answered your questions as follows:\nQ1. You seek confirmation that SP 279 in the IMDG Code and the “+” sign in Column (1) of\nthe HMT assigns the UN Number, Proper Shipping Name, Hazard Class, and Packing\nGroup (PG) to shipments of UN2078, but not to products containing toluene\ndiisocyanate.\nA1. Your understanding is correct. Special Provision 279 and the “+” in Column (1) apply to\nthe listed material, and do not extend to all mixtures or solutions that contain the material.\nIt is the responsibility of the shipper to classify mixtures and solutions of toluene\ndiisocyanate taking into account the classification criteria within the IMDG Code and the\nHMR.\nQ2. You ask whether the UN Model Regulations and the IMDG Code classify “UN2078,\nToluene Diisocyanate, Class 6.1, PG II” as a toxic-by-inhalation hazard (TIH) material.\nA2. The answer is no. Neither the UN Model Regulations or the IMDG Code specifically\nidentify UN2078 as a TIH material.\nQ3. You ask whether a hazard classification under the UN Globally Harmonized System of\nClassification and Labelling of Chemicals (GHS) takes precedence over the hazardous\nclassification criteria of the various hazardous material transportation regulations (e.g.,\nthe HMR, IMDG Code, etc.).\n\n<<<PAGE 2>>>\n\nA3. The answer is no. For purposes of transportation within the United States, the\nclassification criteria in the HMR take precedence over other standards, unless expressly\nauthorized for use. For example, § 171.22 provides authorization and conditions for the\nuse of international standards and regulations.\nSincerely,\nShane C. Kelley\nShane Kelley\nDirector,\nStandards and Rulemaking Division\nOffice of Hazardous Material Standards\n\n<<<PAGE 3>>>\n\nCasey\nJanuary, Ikeya CTR (PHMSA)\n19-0077\nFrom:\nINFOCNTR (PHMSA)\nSent:\nThursday, June 13, 2019 4:45 PM.\nTo:\nHazmat Interps\nSubject:\nFW: UN2078, Toluene Disocyanate, 6.1, II in Mixture(s)\nAttachments:\nToluene Diisocyanate letter.docx; TDI DG fin -model and measured data v.xlsx; TDI DG\nPresentation LXS Solutions May 2018.pptx\nHello Alice and Ikeya,\nPlease see the attached documents for a letter of interpretation request.\nSincerely,\nLynsie, HMIC\nFrom: Marcel, Ernest [mailto:Ernest.Marcel@lanxess.com]\nSent: Tuesday, June 11, 2019 2:18 PM\nTo: INFOCNTR (PHMSA) <INFOCNTR.INFOCNTR@dot.gov>\nSubject: UN2078, Toluene Disocyanate, 6.1, II in Mixture(s)\nTo whom it may concern:\nI would like to submit the attached letter and documents as for a formal letter of interpretation. If further\ninformation is needed, please don't hesitate to contact the undersigned.\nBest Regards,\nHead, Dangerous Goods\nErnest J. Marcel, CDGP, DGSA\nTransportation Compliance\nPTSE/PSRA Group\nLANXESS Solutions, US, Inc.\nOffice Phone: 203.573.2057\n2 Armstrong Road, Shelton, CT 06484, USA\nMobile Phone: 203.558.3408\nWebsite: www.lanxess.us\nernest.marcel@Lanxess.com\n\"Live Safe, Work Safe\"\n\n<<<PAGE 4>>>\n\nLANXESS\nEnergizing Chemistry\nLANXESS Solution, Inc.\nEmest J. Marcel, CDGP, DGAC\nTransportation Compliance\nHead, Dangerous Goods\nLANXESS Solutions, Inc\nPTSE/HSEQ\n: Armstrong Roa\nPhone Office: 203.573.2057\nShelton, CT 06484 US/\nMobile: 203.558.3408\nwww.us.lanxess.com\nEmail: emest.marcel@lanxess.com\n10 June 2019\nPipeline & Hazardous Materials Safety Administration (PHMSA) -U.S. DOT\nOffice of Hazardous Materials Safety, International Standard Program\n1200 New Jersey Avenue S.E., E24-422, Washington D.C. 20590\nE24-422\nRe: UN2078, Toluene Disocyanate, 6.1, Il in Mixture(s)\nTo Whom it my concern:\nLanxess Solutions is requesting an interpretation letter on international classification of UN2078,\nToluene Disocyanate, Class 6.1, Il in mixture(s).\nUN2078 is listed in the 172.101 with a \"+ sign in Column 1 and has SP279 in the UN\nRecommendations and the IMDG Code.\n2.0.2.9 for Classification of mixtures or solutions which states:\n\"A mixture or solution, containing one or more substances identified by name in this Code or\nof this Code, is not subject to the provisions of this Code if the hazard characteristics of the mixture or\nclassified under an N.O.S. or generic entry and one or more substances not subject to the provisions\nclass\"\nsolution are such that they do not meet the criteria (including human experience criteria) for any\nLanxess used a mathematical calculations methodology for the classification of the product. A team\nteam determined that with less than 5% of UN2078 in the mixture that the product did not meet the\nconsisting of two toxicologists and a chemist were assigned to develop and run the calculations. The\nhazardous materials classification requirements of 49CFR, the UN Recommendations or the IMDG\nCode. As a result of this testing Lanxess has been moving this product as non-hazardous for over\nten years.\ntold the following:\nRecently there have been challenges to this classification from an international source. We are being\nPage 1 of 2\n\n<<<PAGE 5>>>\n\nLANXESS\n. Energizing Chemistry\nThat the SP279 means that any product with UN2078 in it must always move using\nthe hazardous classification even if it does not meet the criteria for any hazard\nclass.\nIt is our understanding that SP279 only assigns the UN Number, Proper Shipping Name, the Hazard\nClass, and the Packing Group to UN2078. There are no further restrictions mentioned in SP279.\nRecommendations 2.0.2.7 or the IMDG Code 2.0.2.9 then the product would not be listed as\nIf it is determined that the product is not hazardous per the Classification criteria in the UN\nUN2078. (However, it does require UN2078 to be properly listed as one of the chemicals in the\nmixture on the SDS form). Is our understanding of SP279 correct?\n2. That UN2078 is a Toxic Inhalation Hazard (TIH) per the UN Recommendations and\nthe IMDG Code.\nChecking the latest versions of both documents; neither shows UN2078 as a (TIH). Has UN2078\nbeen updated to say that it is a TIH?\n3. GHS is mentioned multiple times in regards to UN2078 being a TIH and stating that\nGHS over rules the various hazardous material transportation regulations.\nWould GHS classification criteria inhalation hazard take precedence over criteria found in\nChapter 2.6 of the IMDG Code when classifying a material for transport? Issues in the work\nplace are very different from those found in the transportation of hazardous materials.\nWe have attached the following documents for your reference:\n• Latest version of the calculation method to determine the packing group for TDI in Urethane\nPrepolymer\n• TDI DG Presentation\nIf further information is needed, please don't hesitate to contact the undersigned. I can be\nreach by office phone: 203.573.2057, mobile: 203.558.3408 or email at:\nemest.marcel@lanxess.com\nThank you very much for your attention in this important subject matter\nSincerely,\nHead, Dangerous Goods Transportation Compliance\nErnest J. Marcel, CDGP, DGSA\n..\nLANXESS Solutions, Inc.\nPage 2 of 2\n\n<<<PAGE 6>>>\n\nother. (LC50 - (48 mg/Ll There way nu sign ficant difference urmen the LC50 of mal:\nsustains uding tables are houser\nnale/femal-\n66 ppm\ntest mat\n= 31--141\nand female rois.\n3. Using the vapor method with measured data and applying a 95% confidence interval and the LC50 above -> PG III is reached at % TDI ~ 6.1 wt%.\nif 001 Key | Experimental result\n2. For Polymer Solutions the vapor pressure of the Solute is calculated using Flory Huggins Theory (The Ideal Solution Calculation Method is not valid)\n1. Using the vapor method with F-H Polymer Solutions Theory and the LC50 above →- PG Ill is reached at % TDI ~ 40 wt%.\n2. Using measured vapor data and extrapolating from there using the LC50 above → PG III is also reached at % TDI ~ 40 wt%.\nResults and discussion\nEllect levels\nEffectleret\nBered on\n95% CL\nisp. durstion\nRemarks on result\n4. For the Mist /Dust method and the LC50 above →- PG Ill is achieved at %TDI < 32 wt% TDI in a Polymer Solution\nMortality:\nPolymer Solutions containing TDI monomer are not DG if % TDI monomer is < 5wt.%\n3. To be EXTRA conservative the cut-off is set to 5.0 wt%\nSUMMARY and CONCLUSIONS\n1. The LC50 for Rat is 66 ppm (ml/m3)\nCONCLUSION:\n\n<<<PAGE 7>>>\n\nEnergizing Chemistry\nQUALITY WORKS.\nLANXESS\n\n<<<PAGE 8>>>\n\nLANXESS\n• Transportation and Distribution\n• Stakeholder Communication\n• Product Stewardship\n• Community Outreach\n• Emergency Response\nRC and GPS are both global initiatives to improve the chemical industry's environmental,\nPrinciples\nhealth, safety, and security performance.\n• New Product and Process Devel\nOur Company Commitment\n• Human Health and Safety\n• Environmental Protection\n• Process Safety\n• Product Safety\n• Security\n\n<<<PAGE 9>>>\n\nLANXESS\n- Calculating Vapor Pressure and Mist Concentration of TDI in Polymer Solutions.\n• Concentration at which TDI in Polymer Solutions is Packing Group III\n• Is Solvent Methodology Applicable for TDI in Polymer Solutions?\n• Assessing DG Classification of TDI in Simple Solvents\nOutline\n\n<<<PAGE 10>>>\n\nREACH Dossier\n66\nRat\n66\nLANXESS\nConvert to 1 hr duration:\nEstablish LC50 in mg/Lfor TDI\nReference\nLC50 (ppm)\nDuration (hours)\nCorr Factor to 1 hour\nCorrected LC50 vapor\nSpecies\non LC so daya relating\none on 1C so data\nIf V ≥ IC so and LCso ≤ 3 000 ml/m'. and not meeting the criteria\nIF V ≥ 1/5 Lso and LCso ≤ 5000 ml/m?. and not meeting the\nDangerous Goods - Criteria for Determining Packing Group\nLiquids having toxic r'apours shall be assigned to the following packing groups. where \"V is the\nIf V ≥ 10 LCso and ICso ≤ 1 000 ml/m':\ncriteria for packing groups I or II.\nIn Figure 2.6.1. the criteria according to 2.6.2.2.4.3 are expressed in graphical form. as an aid to\nCopyront@unted Nanot 201: All mont: deserved!\nThe critera for inhalation toxicity of dusts and mists in 2.6.2.2.4.1 are base\nrelating to 4 hours exposures to dusts and mists are available, such figures can be multiplied by four and the\nproduct substituted in the above criteria. i.e. LC so (4 hours) × 4 is considered the equivalent of LCso (1 hour).\nsaturated vapour concentration in millilitres per cubic metre of air (volatility) at 20 °C and standard atmospheric\nfor packing group I:\neasy classification. However, because of approximations inherent in the use of graphs. substances on or near\nto 1 hour exposures and where such information is available it shall be used. However.\nTDI LC50 (1 hr) = 66 ppm\nPacking group II:\npacking group borderlines shall be checked using numerical criteria.\n(a) Packing group I:\n(c) Packing group IT!:\n(b)\n2.6.2.2.4.2\n2.6.2.2.4.3\npressure:\n2.6.2.2.4.4\n\n<<<PAGE 11>>>\n\nLANXESS\nVapor\nLiquid\nAssume Solvent MW=174\nTDI = (21(2+68) = 2.9 mole%\nPvapTol in Solvent = Mole% TDI x Pvap TDI TDI at 20c\nProject TRAX\nIf no data available→> Use Calculation Method for Determining Packing Group\n100 wt% = 100 mole% TDI\nPvapor of TDI in Simple Solvent\n(ml/m3)\nPVapTo= 20.7 ppm\nLiquid 100% TDI\nVapor\nat 20 °C\nPrapor\n\n<<<PAGE 12>>>\n\nLANXESS\nPolymer\n2 molecules TDI per 1 long molecule\nPolymer → 21(2+1) =67 mole% TDI\nassume Polymer Solution is\nPvap Tol in Solvent = Mole% TDI x Pvap 100% TDI at 20C\nProject TRAX\nTDI in Simple Solvent vs. TDI in Polymer Solution\n2.9 mole% TDI in Solvent\n(2 TDI for 68 solvent molec)\nMW TD=174.16\nLiquid\n\n<<<PAGE 13>>>\n\nLANXESS\nPolymer\n5.6 wt% TDI but assume Polymer\n1 moleculePolymer → 67 mole% TDI\nSolution is 2 molecules TDI per\nSIMPLE SOLUTE/SOLVENT THEORY IS NOT CORRECT FOR SOLUTE/POLYMER SYSTEMS\nProject TRAX\nPvaPTDI in Solvent = Mole% TDI x Pvap 100% TDI at 20c\nTDI in Simple Solvent vs. TDI in Polymer Solution\n2.9 mole% TDI in Solvent\n(2 TDI for 68 solvent molec)\nMWTD=174.16\nLiquid\n\n<<<PAGE 14>>>\n\nLANXESS\nPapToI = a, Pvap 100% TDI\nSolute - Polymer Interaction Parameter and is always positive. M\nMaximum value (before incompatbility = phase separation) = 0.5\nMolar Volume Ratio of Polymer/Solute\nSee Spreadsheet for Calculation Details and Parameter Values\nFor a two component system such as we have here per Flory-Huggins, the activity of the Solute (= a1) in the Polymer =\nvolume fraction of polymer\nProject TRAX\ngr/cm3 for range 25C to 40C\nThe proper variable for calculating Pvap of solute (=TDI) in Polymer Solution\ngr/cm3 at 25C\nRather... Use Flory - Huggins Polymer Solution Theory\nФ. +2,Ф:\nis a function of VOLUME % .... not MOLE %\n1.21\n1.07\n%:\nBasically ...\nDensity of TDI\nDensity Adiprene\nwhere\n\n<<<PAGE 15>>>\n\nLANXESS\nVolatility = (Pvap × 10º) / 101.3\nPDF\nVolatility [=ml/m3] [= ppm]\n[=kPa]\nNot DG if Volatility TDI from\nTDI in Polymer Solution\nis < 12 ppm\nPvap\nLCSO =\n56 ppm\nDangerous Goods Cut-Off Calculation and Actual Measured TDI Partial Pressure Results\n100 000\nPACKING GROUP I\nPACKINC CROUP I\nPACKING GROUP T\n10 000\n1 000\nFigare 2.6.1: INHALATION TONICITY: PACKING GROIP BORDERLINES\nCalculated and\nMeasured Volatility\nVolatility ml/s\n100\nNOT DANGEROL'S\n12 ppm\nFOR TRANSPORT\n10 000\n1000-\nI.Co. mlini\nA = measured\n\n<<<PAGE 16>>>\n\n100\nLANXESS\nV\n~40%\n- 95% CI\n• Modeled\n+ 95% Cl\n10\nwt% TDI in Polymer Solution\n~ 6%\nPG HIT\nNot DC →\nMeasured\n15.0\n14.0\n13.0\n12.0\n110\n10.0\n9.0\n8.0\n7.0\n6.0\n5.0 +\n4.0 +\n3.0 -\n20-\n1.0 $\n0.0 +\nml/m3 (=ppm)\nTDI Volatility\nProject TRAX\nEstablishing the Cut-Off for TDI in Polymer Solutions\n5.7\n11.7\n+/_ 95% Confidence Intervals\nof measured values\n3.1\n2.6\nMeasured and F-H Calculated Volatility Values\nMeasured\n4.1\n5.6\nConclusion: Based on Measured Data for\nFree TDI in Polymer Solutions the DG Cut-Off\nCalculated F-H\nTheory\n0.7\n1.4\n2.8\n5.0\n8.4\nis set extra conservatively at 5 wt.%\nIf wt% TDI in\nPrePolym =\n5.3\n16\n\n<<<PAGE 17>>>\n\nLANXESS\nReference Book Chapter on Flory Huggins Polymer Solution Theory\nProject TRAX\nNotes - for additional details see the embedded Spreadsheet\n1. For mists the cut-off is higher, therefore the vapor pressure method is used\n2. TDI becomes PG Il when it is almost pure (=100% TDI).\nDetailed calculations\nto set the cut-off (see spreadsheet for details).\nMicrosoft Excel\nWorksheet\nMicrosoft Word\n97 - 2003 Document\n\n<<<PAGE 18>>>\n\nEnergizing Chemistry\nLANXESS\nQUALITY WORKS.","truncated":false,"body_characters":14670}