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

FR market

3

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

Hordaresin is used as a

Flame Retardant in

Plastics

Rubber

Processing Aid

Filler Coupling Agent

The stability of solid chlorinated paraffin

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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.

Polymer without CP/SB2O3

Polymer with CP/SB2O3

PASSES STEINER TUNNEL TEST!!!

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?

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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

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Chlorez® / Hordaresin® Resinous Chlorinated Paraffins

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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

Test protocol T = 0

End of test 20 mins

Intumescent with CP Hordaresin NP70

Intumescent without CP

Hordaresin NP70

Hordaresin NP70 + P145

Hordaresin CH151

Hordaresin CH171

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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

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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

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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

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Heat Stability Test @220°C Dover

Hordaresin NP70

Competitor

Sample

5 mins.

10 mins.

15 mins.

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

Dover Chemical Company

Additives with problems due to REACh

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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

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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.

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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).

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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.

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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

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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)