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Who is Dover Chemical? Largest manufacturer of chlorinated paraffins, olefins
and esters
Largest producer of solid CP resin
Largest liquid organophosphite producer
Leading manufacturer of metalworking fluid additives based on Sulphur, Chlorine and Phosphorus
ISO 9001 certified manufacturer
Chlorinated Paraffin CP’s Short chain SCCP – C10-13
Medium Chain MCCP – C14-17
Long Chain LCCP – C18+
SCCP and MCCP are liquids – never used in intumescent coatings
LCCP is a liquid at low Chlorine and solid at high chlorine levels typically 70% for solid
MEDIUM CHAIN Chlorinated Paraffins, C14-C17
Product
Color, Typical
Gardner (1933 Std.)
Chlorine Content %
by Wt.
Specific Gravity @ 25°/25°C
Viscosity Poises @
77°F
Viscosity SUS @ 210°F
Density, Pounds Per
Gallon
Volatility % Loss, 25 hrs.
@ 100°C
Stability: JQD
Method %HCl, 4 hrs.
@ 175°C
Flash Point °F (Cleveland Open Cup)
Paroil®
10-NR <1 40.8 1.113 0.37 35 9.3 8 0.2 >350
45 1 45 1.18 2.5 48 9.6 1.5 0.2 >400
152 1 51 1.27 15 70 10.3 0.9 0.2 >450
51-NR N/A 51 1.23 N/A 56 10.2 N/A N/A >450
53-NR 1 53.7 1.292 14 71 10.8 1 0.2 >450
54-NR 150
APHA max
54 131 N/A 74 10.9 N/A N/A >450
56-NR 300
APHA max
56.0 1.32 85 - 135 110 - 135 11.0 0.02%
(typical) 0.3
(typical) >450
58-NR 1 59 1.39 271 172 11.6 0.5 0.2 >450
63-NR 1 62 1.4 450 310 11.6 0.5 0.2 >450
Chlorowax®
S-52 1 52 1.261 16 71 10.5 0.9 0.2 >450 5
LONG CHAIN liquid Chlorinated Paraffins, C20+
Product
Color, Typical
Gardner (1933 Std.)
Chlorine Content %
by Wt.
Specific Gravity @
25°/25°C
Viscosity Poises @
77°F
Viscosity SUS @ 210°F
Density, Pounds Per
Gallon
Volatility % Loss, 25 hrs. @ 100°C
Stability: JQD
Method %HCl, 4
hrs. @ 175°C
Flash Point °F
(Cleveland Open Cup)
Paroil®
140 1 42 1.17 29 150 9.6 0.8 0.3 >450
140 LV 1 42 1.17 26 142 9.5 0.18 .016 >450
140-LVXS
142-LV 2-3 43 1.175 38 160 9.6 0.8 0.35 >450
142 2-3 45.5 1.215 70 200 9.9 0.8 0.4 >450
145 2-3 46.5 1.22 95 230 10 0.8 0.5 >450
150-LVA 2 48 1.24 130 270 10.3 1 0.25 >450
150-LV 2-3 51 1.275 180 245 10.4 1 0.45 >450
150 2-3 50 1.26 375 450 10.3 1 0.5 >450
500 2 53 1.3 - 670 10.8 - -
Chlorowax®
41-SW 3 42 1.168 24 130 9.7 0.5 0.3 >450
40 2 43 1.17 27 140 9.7 0.8 0.4 >450
50 3 48 1.23 110 230 10.2 0.8 0.5 >450 6
Long Chain Solid Chlorinated Paraffin Hordaresin
Dover offer three main qualities based on stability under the trade mark Hordaresin
Standard - NP70
Medium - CH151 Processing at 180 C High - CH171 Processing at 210 C
The difference is mainly measured by heat stability
All three grades conform to EU legislation on chlorinated impurities such as CCL4 and Chlorinated aromatics
Flame Retardant Properties
Hordaresin works as a flame retardant by releasing HCl which quenches
flames. In systems containing antimony trioxide, HCl further reacts by the
following reactions, which also inhibit flames:
Sb2O3 + 2 HCl 2 SbOCl + H2O 250°C
5 SbOCl Sb4O5Cl2 + SbCl3 245 - 280°C
4 Sb4O5Cl2 5 Sb3O4Cl + SbCl3 410 - 475°C
3 Sb3O4Cl 4 Sb2O3 + SbCl3 475 - 565°C
These reactions are endothermic, leading to cooling of the system. In addition,
SbCl3 forms a heavy vapor which helps to smother flames.
Hordaresin as a Flame Retardant in Plastics
More cost effective than Brominated flame
retardants
Less thermally stable - used for low
shear/process temperatures
HIPS, LDPE film, PE foam, rubber
UV Stability Hordaresin versus Decabrom
Acclerated Fluorescent Light Exposure in HIPS Formulation
0
5
10
15
20
25
30
35
0 5 10 15 20 25
Days of Exposure
Co
lor
(YI)
Hordaresin
Decabrom
Solvent based Intumescent
Although chlorine and intumescent based flame retardant systems are antagonistic solid chlorinated paraffin's is used in all 60+ minutes intumescent coatings……why?
15
Solvent % Upper Limit solubility Xylene 65-70
Toluene 65-70
Chlorobenzene 50
Trichloroethylene 50-60
Carbon tetrachloride 55
Chloroform 55
Methyl Ethyl Ketone 65-70
Ethyl Acetate 50
Acetone 55
Mineral Spirits 20-50 (depending on grade)
Methanol insoluble
Butanol insoluble
Ethanol insoluble
Isopropanol insoluble
Ethylene glycol insoluble
16
Chlorez® / Hordaresin® Resinous Chlorinated Paraffins
17
Product Physical Form
APHA Color
Chlorine Content % by Wt.
S.G./25°C
Particle Size, % Thru 50 Mesh
Volatiles
S.P., °C (Ball & Ring Method)
Stability, JQD, % HCl 4 hrs. @175°C
Chlorez 700 White Powder
150 71.5 1.6 95% < 0.1% 103 0.1 Hordaresin NP-70
Chlorez 700-S White Powder
100 71.5 1.6 95% < 0.1% 103 0.05 Hordaresin® CH151
Hordaresin® CH171F
White Flake
125 71 1.6 Flake < 0.1% 103 0.01
Measurements taken Foam - average foam height in mm
Reserve - not foamed fire protection
Voids - foam without defects (without larger bubbles)
Expansion rate - foam height
October 21, 2011 Canada CP Schedule 1 Update 30
time none 1.5mm CH151 CH171 Chlorinated
SA
NP70 +
P145
NP70
+ZnSt NP 70 NP 70
foam height 27 28 3 25 22 25 35
Reserve 2 2 0 3 ≤ 2 ≤ 2 23
voids few few one one few none
Expansion ~36 ~35 31 30 29 40
Appearance fine pores fine pores carbonised fine pores fine pores fine pores fine pores
cut resistent resistent resistent resistent resistent resistant
31
Conclusion
Solvent based intumescent coating can achieve higher fire protection ratings with the addition of a solid chlorinated paraffin
Solid chlorinated paraffin are more than blowing agents they help to give a char foam structure
Hordaresin NP70 gives the best intumescent foam of all CPs
32
Water based Intumescent CP is usually only for 120 minute protection, so most
formulations are without CP.
With binder with a higher molecular weight. CP in water based materials makes a soft foam with slumping.
CP are insoluble in water (swimming pool paints, tent protection)
CP’s readily emulsify
33
Chlorinated Paraffin what to look for
%Cl Legislation requires 70% minimum
Stability/JQD Jefferson quartermaster department - M*A*S*H* 2HRS@185°C. Caustic wash (note water wash gives half real level)
Color light yellow
S.P. Softening point
%CCl4 legislation 0.1% Maximum
Additives with problems due to REACh
37
Annex 17 Restrictions* lists these FRs:
Pentabromodiphenyl ether (PentaBDE, 0,1% w/w)
Octabromodiphenyl ether (OctaBDE, 0,1% w/w)
Not allowed in articles for skin contact (e.g. textiles):
Tris(aziridinyl)phosphinoxide
Tris (2,3 dibromopropyl) phosphate (TRIS)
Polybromobiphenyls (PBB)
Annex 14 (Candidate) List of Substances of Very High Concern for Authorisation:
Hexabromocyclododecane (HBCD) – PBT substance
Tris(chloroethyl)phosphate (TCEP) – Reprotox Cat. 1b
Alkanes, C10-13, chloro (Short Chain Chlorinated Paraffins) - PBT and vPvB
Boric Acid - Reprotox
Human Health Issues CP’s generally have low toxicity
Carcinogenicity considered the main health effect of concern for SCCP
NTP tested both a SCCP and LCCP; only the C12, 60% CP is considered to be carcinogenic to laboratory animals
Recent mechanistic studies demonstrate that most of the animal tumors are not relevant to man. Outstanding issues remain regarding the kidney.
USEPA concluded that LCCP should not be classified as a potential carcinogen.
Environmental Concern Low concentrations of SCCP’s found to be toxic to
aquatic organisms.
Concern about persistence and bioaccumulation
Recent studies show that persistence in the environment maybe significantly overstated.
MCCP’s and LCCP’s are typically not associated with environmental toxicity, MCCP is biodegradable
CPIA is addressing outstanding concern regarding Daphnia studies on MCCP
Topics Canada
CEPA Schedule 1
USA
Chemical Action Plan - SCCP’s
TSCA Inventory
European Union
REACH
United Nations
POPRC
40
Canada CP Activiites • July 2011 – Canada proposes to add C10-C13 chloroalkanes
(SCCP) to the prohibited substances list.
▫ Dover did not challenge.
• September 2011 – Health Canada announces that C18+ chloroalkanes (LCCP) are NOT CEPA toxic to human health; HC/EC propose no further action on >C20 chloroalkanes.
▫ Dover working with Canadian authorities but does not anticipate impact on LCCP usage in Canada.
• October 12, 2011 – Canada Gazette II notice place C10-C20 chloroalkanes on Schedule 1.
▫ Dover working closely with Canada to develop reasonable risk management for MCCP.
42
CP Schedule 1 History
September 2008 – Canada Gazette I notice proposing to place ALL CPs (C10-C38) on Schedule 1 of CEPA 1999 (CEPA Toxic) and CP’s up to C20 on VE list; CPIA comments and files Notice of Objection.
2009-2011 – Various interactions with Canadian authorities over risk assessment, risk management issues.
Canada switches to calling substances chloroalkanes (to eliminate any confusion regarding hydrocarbon feedstocks).
43
July 2011 – Canada proposes to add C10-C13 chloroalkanes to the prohibited substances list. A move that was actually done prior to adding them official to Schedule 1 (CEPA Toxic)
September 2011 – Health Canada announces that C18+ chloroalkanes (long-chain chlorinated paraffins (LCCPs)) are NOT CEPA Toxic to human health; HC/EC propose no further action on >C20 LCCPs
October 12, 2011 – Canada Gazette II notice place C10-C20 chloroalkanes on Schedule 1. No official action on risk management yet.
44
Canada’s CP Schedule 1 History (Con’t)
Schedule 1 – NOT a prohibition
Placement on Schedule 1 is a necessary first step before the development of risk management regulations.
There are hundreds of chemicals on Schedule 1, many that continue to be used in a variety of applications.
Industry can (must) be very involved with the risk management regulations that are developed. The more information provided to Environment Canada, often the better the result.
45
Example of Risk Management 2-Butoxyethanol (EGBE) place on Schedule 1 -
common solvent in paints, cleaners.
Environment Canada allows wildly different use concentrations (apparently based on interaction with downstream industries).
Concentration Limit (%) (w/w)
Automobile Cleaner1 10.0
Rug or Carpet Cleaner 10.0
Floor or Baseboard Stripper 2.0
Paint Stripper or Thinner 0.5
Laundry Stain Remover 22.0
Any Other Aerosol2 Cleaner3 5.0
Any Other Non-aerosol Cleaner3 6.0
Aerosol2 Paint or Coating 0.1
Non-aerosol Paint or Coating 0.5
46
Next Steps with Canada: Work with key industries to develop risk management
plans for the C14-C20 chloroalkanes, primarily focusing on the C14-C17 (MCCP);
Goal will be to support “workable” risk management (not a prohibition or restriction) and any use exemptions.
Resolve definitional issues with LCCP regarding constituents <C21.
47
New information Canada: CPs biodegrade in Canadian river water in less than a year
Canada Health publish work and state Sept 2011
Based on information presented, LCCPs are not entering the environment or under conditions that may constitute a danger to human life or health as defined in the paragraph 64© of the CEPA 1999
48
USA Chemical Action Plan on SCCP
For purposes of this action plan, short-chain chlorinated paraffins (SCCPs) include all individual chemicals or mixtures that contain: CxH(2x-y+2)Cly where x = 10-13; y = 3-12; and the average chlorine content ranges from approximately 40 to 70 percent with the limiting molecular formulas set at C10H19Cl3 and C13H16Cl12.
EPA intends to initiate action under TSCA section 6(a) to ban or restrict the manufacture, import, processing or distribution in commerce, export, and use of SCCPs.
50
USA (con’t) CP TSCA Inventory Issues/PMNs
In conducting its review of chlorinated paraffins, EPA determined that some of the specific SCCPs, MCCPs, and LCCPs currently being manufactured and/or used in the United States are not on the TSCA Inventory. Any substance that is not on the TSCA Inventory is classified as a new chemical. Prior to manufacture or import of a new chemical for general commercial use, a notice must be filed with EPA under TSCA section 5.
EPA intends to require companies to submit Pre-Manufacture Notices for the SCCP, MCCP, and LCCP fractions that are not on the TSCA Inventory.
51
Chemical Action Plan • EPA started posted chemical action plans (CAPs) in 2009
on priority substances for review. ▫ SCCP CAP was among first.
• SCCP 2009 CAP mentions concerns that SCCP is a persistent, bioaccumulative, and toxic (PBT) substance and discusses the possibility of actions under TSCA section 6a to ban or restrict its manufacture, import, processing or distribution, export, and use.
• EPA also mentions TSCA Inventory concerns in the CAP and that it intends to require companies to submit Pre-manufacturing notices (PMN’s)for the SCCP, MCCP, and LCCP fractions that are not adequately covered by existing substances on the TSCA Inventory.
52
Dover Consent Decree • Resolves previous Notice of Violation (NOV)
regarding TSCA Inventory.
• Requires: ▫ No future production of SCCP
▫ Submission of PMNs for MCCP and LCCP
• Allows for continued production of MCCP and LCCP with timely (30-day) PMN submitted.
• Provided Dover with the best means of resolving issues with EPA and moving forward with the CP business.
53
Next Steps for MCCP and LCCP • PMNs for MCCP and LCCP are underway and will be
filed within deadline from consent decree.
• Substances have been very well tested and recently assessed by Canada, EU, OECD, etc.
• Dover believes there is adequate information to support that MCCP and LCCP are not PBT substances. ▫ LCCP recently (Oct. 2009) reviewed by OECD, which
includes EPA. It concluded LCCP has a low order of toxicity and is not a PBT
▫ MCCP REACH registration, completed in late 2010 and utilizing new data, concludes MCCP is not a PBT.
54
SCCP, MCCP, and LCCP are all registered under REACH
SCCP is on the candidate substances list as a Substance of Very High Concern (SVHC). It’s uses will be closely evaluated by the authorities but it is not technically prohibited (yet).
While MCCP is fully registered under REACH, it is getting some additional evaluation regarding its environmental fate. It is not considered a PBT substance in the EU. New Evidence shows it si biodegradable. The MCCP REACH dossier provides a good technical basis for concluding that MCCP is not a PBT.
56
NEW INFORMATION ON MCCP FROM EUROCHLOR
Assessment of persistence of chlorinated paraffins using OECD biodegradability tests (ready and enhanced)
Tests using Rhine water sludge extracted near Heveadorf
41.2% Cl, 45.5% Cl, - readily biodegradable 50.0% Cl, 60.2% Cl - biodegradable
57
LCCP is fully registered under REACH. It is not classified has hazardous to human health or the environment in the EU.
58
United Nations POPRC SCCP continues to be considered as a
Persistent Organic Pollutant (POP) under the UN Stockholm Convention.
SCCP is not expected to be voted on at this meeting (it was voted down 5 previous times!), though there will be a discussion on a new paper discussing the potential for effects from cumulative/combined exposure to different grades of CPs.
60
Summary: Canada
Risk management plan to be established for MCCP / LCCP’s by end of 2013.
SCCP use will be restricted or banned.
No current restrictions on MCCP / LCCP use.
Published in Health Canada
USA
SCCP use will be restricted or banned
TSCA inventory issues to be resolved by end of 2012
No current use restrictions on MCCP / LCCP
Toxicity Summary: European Union
SCCP, MCCP, LCCP all registered under REACH
SCCP likely to be restricted or banned
LCCP classified as not hazardous to human health or the environment
United Nations
SCCP continues to be considered as a persistent organic pollutant (POP) however it has yet to be voted on. It was voted down on the past 5 attempts
62
Summary of Solid Chlorinated Paraffin (LCCP)
cheap
works
Safe to health
Safe to environment
Survived REACh
Unrestricted
Organo-Chlorine in the environment Site organochlorine source
microg/Kg
North Sea Mud flats 25-125 Greenpeace
Pre industrial lake sediment 30000 - 100000 University of Heidelberg Ancient Black sea sediment 313000 – 465000 University of Heidelberg
F. Keppler et al, Natural formation of vinyl chloride in the terrestrial environment. Environmental
Science and Technology, 36, (2002) 2479 - 2483
G Gribble The diversity of naturally produced organohalogens . Chemosphere 52 (2) 289 -97 (2003)