Dimethyl Carbonate (DMC) - Kowa American Corporation

Report
DIMETHYL CARBONATE
(DMC)
Why aren’t You using it?
Kowa American Corp.
www.chemical.kowa.com
212-303-7800
July 2013
DMC Structure
• Dimethyl Carbonate CAS # 616-38-6
DMC Introduction
• DMC is an inexpensive oxygenated solvent
with excellent solubility properties, that can
solve almost all coating resins.
• DMC is now cheaper than MEK, Ethyl
Acetate, MIBK, Butyl Acetate and most
other Ketones and Glycol Ethers.
• DMC is price competitive with acetone,
toluene, ethanol and mineral spirits
DMC Supply
• Drums and bulk isotanks readily available
from multiple factories in China.
• DMC is used in very large volumes in
China for coatings primarily because of its
low cost.
• Totes can be filled from isotanks.
• Long term a bulk tank in USA is possible
DMC Expected Uses
• DMC has shown promise in Auto refinish
and concrete coatings with its favorable
solubility, odor, evaporation rate and
economic profiles
• Industrial coatings for coating parts and
architectural components at factories have
shown similar appeal.
• Also used in traffic paints, steel drum
linings, floor coatings and architectural
coatings
MEK and TBAC replacement
• DMC is cheaper than both these solvents,
with very similar properties.
• Anyone using these two solvents should be
immediately considering using DMC!
• Only users of TBAC for Canadian market
cannot use DMC as VOC exempt there yet.
PCBTF Replacement
• PCBTF is twice to 3 times the price of
DMC, PCBTF has an objectionable odor
Advantages for Regional
Coatings Manufacturers
• Large National coatings manufacturers
presently do not want to have multiple
formulations in different states and Canada.
• Local and regional coatings companies have
more flexibility to avoid the non-exempt
California districts and Canada thereby
having very cost competitive and superior
products available for sale.
DMC General Properties
• DMC is a colorless, fast evaporating solvent
• Has substantial polar nature, and moderate hbonding strength effective in replacing esters,
glycol ethers and ketones in formulations
• Has low toxicity, an unobjectionable
methanol type odor and low skin irritation
• Freezes at 2 – 4 ºC (36 –38 ºF)
• Flammable Liquid, Flash point 17 ºC (63 ºF)
DMC Evaporation Rate
DMC’s moderate to fast evaporation rate (3.22)
BuAC = 1.0, is similar to tBAC (2.8), isopropyl
acetate (3.0) and the major gasoline components
Heptane (3.18) and trimethyl pentane (3.63)
Can be used to as slightly slower evaporating
replacement for MEK (3.8), Ethyl Acetate (4.1)
Or a faster evaporating replacement for Toluene
(2.0), Isopropanol (1.7), MPK (2.3), Ethanol
(1.8), Methanol (2.1) and MIBK (1.6)
DMC’s Odor Profile
• One of DMC’s most favorable properties is
a mild and non-offensive odor.
• PCBTF and Tert-Butyl Acetate odors are
much more pronounced and pungent
• Noxious solvent odors are perhaps the most
important concern of neighbors to body
shops, factories, print shops and other
industrial settings
• Mild odor is well received by workers
handling DMC or used in their work areas
DMC Solubility Properties
• Hildebrand solubility parameter 20.3 Mpa
• Hansen solubility parameters: Dispersion
15.5 polar 3.9 h-bond 9.7 molar vol. 84.2
• Almost identical solubility parameters to
some common glycol ethers: cellosolve
acetate, ethylene glycol butyl ether acetate,
propylene glycol monobutyl ether.
• Ethyl acetate, 2-ethylhexanol, methylene
chloride and MIBK have similar solubility
parameters
DMC Solubility Properties
DMC has been described as useful in acrylics,
urethanes, epoxies and alkyd systems.
DMC is miscible with almost all organic
solvents
DMC would easily replace oxygenated
solvents like esters, ketones & glycol ethers
DMC can replace alcohols, aromatics and
aliphatics with appropriate co-solvents
and/or reformulation work
DMC - Flammability
• DMC has a flashpoint of 63ºF (17ºC)
• Flammability will limit use in consumer
coatings, cleaning or indoor applications
• Flammability risk still much lower than
acetone (-4º F), ethyl acetate (26ºF) or MEK
(26ºF), which DMC can readily replace
• Partially water soluble (up to 13 % in
water), which allows water to be more
effective in fighting DMC based fires.
DMC in Waterborne Systems
• DMC being an ester, can hydrolyze in
acidic and basic aqueous conditions to
methanol and carbon dioxide.
• DMC may be stable in neutral conditions
with suitable buffers.
• DMC’s primary usage area should be in
solvent borne systems, where residual water
does not normally cause hydrolysis issues
DMC is VOC Exempt
• Dimethyl Carbonate (DMC) & Propylene
Carbonate were exempted as VOC’s by EPA on
Jan 13, 2009 based on Kowa’s petition to EPA in
July 2004.
• Each state besides California must also exempt
DMC for stationary source VOC rules.
• All states (besides CA) have either exempted
DMC or allow for enforcement discretion
(Kansas & Michigan) or allow individual stationary source permits for DMC’s use (Arkansas).
DMC for Architectural &
Automotive Refinish Coatings,
DMC is VOC exempt in all states today except
for parts of California (see slides 22 & 23) for:
Architectural Coatings (subpart D),
Automotive Refinish Coatings (Subpart B)
DMC is exempt as a VOC in all states except for
California for consumer items (subpart C)
Based on Federal VOC rules (40 CFR part 59)
DMC VOC Exempt States
Washington
March 2011
Montana
Oregon
May 2010
Vermont
Maine
Minnesota
Idaho
March 2010
New Hampshire
Wyoming
Oct. 2010
Nevada
North Dakota
California
Each AMD
must exempt
New
Mexico
Kansas
Sept. 2010
Oklahoma
July 2010
Indiana
Texas
April 1, 2010
New Jersey
Ohio
West
Virginia
Delaware
Maryland
Arkansas
July2013?
North Carolina
South Carolina
Nov. 2010
Georgia
Louisiana
Florida
Hawaii
Virginia
Kentucky
Tennessee
August 2010
Alabama
March
2010
Alaska
Dec. 2010
Massachusetts Feb. 2013
Rhode Island
Connecticut
Pennsylvania
Iowa
Missouri
Dec. 2010
New York
Dec 2010
Michigan
Illinois
Colorado
Arizona
August 2012
South Dakota
June 2010
Nebraska
June 2010
Utah
March 2010
Wisconsin
Aug. 2010
Green states allow
use of DMC as
VOC exempt
with no restrictions.
Arkansas users
must file for
Stationary source
permit until fully
exempted in July
DMC in Aerosol Coatings
• DMC is allowed for use in aerosol coating in
all of California using its MIR of .06 for the
weighted reactivity calculations.
• Effective June 7th, 2012 DMC is now allowed
in Aerosol Coatings for the rest of the USA
again using its reactivity factor of .06.
• This ultra low reactivity factor means almost
zero contribution to the final weighted average
by using DMC in an aerosol coating.
DMC Exemption Status in Calif.
• San Joaquin Valley, San Diego, Sacramento,
Monterey Bay, Mohave, Butte ,Ventura, YoloSolano, Shasta, Colusa & Feather River AMD’s
have exempted DMC as a VOC with no
restrictions on use.
• There are no VOC rules in most northern and
mountain AMD’s (DMC functionally exempt)
• Glenn, Tehema & San Luis Obispo AMD’s may
require a variance for some stationary sources.
• Santa Barbara users must file for a permit
DMC SCAQMD
• South Coast AQMD (Los Angeles area) has
issued a proposed metal coatings rule 1107
allowing for no permit for volumes under
180,000 lbs per year, permits required for
above this threshold. There will be reporting
requirements for all users in SCAQMD.
• After this rule has been approved, we will
request DMC to be exempted for all uses here,
since proposed rule treats DMC as safer to use
than TBAC (560 lb permit threshold)
Bay Area, Tehema, Imperial AMD’s
• BAAQMD plans to publish a proposed rule
exempting DMC as a VOC this summer.
Initial indications are that permits will not
be required. Also TBAC will not be
included in this proposed rule
• Imperial and Tehema plan to move forward
with a proposed rule in July time frame with
no restrictions
Del
Norte
Siskiyou
Modoc
Shasta
Trinity
Green = DMC VOC Exempt or
Functionally Exempt/ no VOC rules
(no restrictions on use of DMC for
architectural coatings)
Lassen
Tehama
Yellow = DMC cannot be used as
VOC exempt for Architectural
coatings
Plumas
Butte
Glenn
Sierra
Nevada
Colusa
Lake
El Dorado
Yolo
Alpine
Napa
Amador
Sonoma
Solano
Marin
San
Contra Joaquin
Tuolumne
Costa
San Francisco
Light Blue = In rulemaking or
preparing rule, DMC cannot be
used for Architectural Coatings yet
Mono
Alameda
San
Mateo
Santa
Santa
Clara
Merced
Cruz
San
Benito
Fresno
Inyo
Tulare
Monterey
Kings
San Luis
Obispo
Kern
San Bernardino
Santa
Barbara
Los
Ventura Angeles
Dimethyl Carbonate (DMC)
VOC Exempt
Status for Architectural
Coatings only
Orange
Riverside
San Diego
Imperial
Del
Norte
Siskiyou
Modoc
Shasta
Trinity
Green = DMC VOC Exempt or
Functionally Exempt/ no VOC rules
(no restrictions on use of DMC)
Lassen
Orange = permit or application for
individual variance may be
required depending on DMC’s use
Tehama
Plumas
Butte
Glenn
Sierra
Nevada
Colusa
Lake
El Dorado
Yolo
Alpine
Napa
Amador
Sonoma
Solano
Marin
San
Contra Joaquin
Tuolumne
Costa
San Francisco
Light Blue = DMC in rulemaking
(not VOC exempt yet)
Yellow = DMC not VOC exempt
Mono
Alameda
San
Mateo
Santa
Santa
Clara
Merced
Cruz
San
Benito
Fresno
Inyo
Tulare
Monterey
Kings
San Luis
Obispo
Kern
San Bernardino
Santa
Barbara
DMC VOC Exempt
status for Car
Refinish and
Stationary sources
Los
Ventura Angeles
Orange
Riverside
San Diego
Imperial
California CARB Consumer items
• CARB regulates “consumer product” applications
(coatings are covered by each AQMD separately)
• Paint thinners are in CARB’s “multi-purpose
solvent” classification for all thinners not used
exclusively for a specific coating and sold
together with that coating.
• CARB presently has no plans to exempt DMC as
a VOC in consumer products although their
proposed Paint thinner rules will now effectively
allow only acetone and PCBTF in paint thinners.
Paint Thinner in OTC States
• DMC being exempt in all of the OTC states
will be a perfect solvent for use in 2014 when
the OTC paint thinner and multi-purpose
solvent rules come into effect.
• These strict limits patterned after California’s
CARB solvent rules are very burdensome for
California businesses and residents, DMC
will allow considerable leeway in meeting
these VOC limits in the OTC & other states.
Canada
• Canada has a proposed rule under
development that updates their VOC
exempt list to be harmonized with the USA
VOC exempt list.
• Proposed rule covers all of Canada, there
will no separate approval process needed
for each province.
• Rule is expected to be out for public
comment in July
DMC – Toxicity
• DMC (like all methyl esters) rapidly deesterifies in the body to methanol & CO2
• DMC has low acute oral toxicity (LD50 rat
12,900 mg/Kg, LD50 mouse 6,000 mg/Kg)
• DMC was found to be negative in mutagenic
tests (in vitro Ames & comet assay)
• Readily biodegradable and has low potential to
bio-accumulate or be persistent in environment
• Not expected to be toxic to fish or bacteria
(possibly toxic to algae)
DMC & Methanol toxicities
• Kowa recommends an 8 hour industrial PEL of
100 ppm based on DMC’s toxicity profile and
that of its metabolite Methanol. This is similar to
the TLV exposure restrictions of Toluene.
• DMC has small amounts of methanol impurities
(normally under 100 ppm), which has recently
been declared a Proposition 65 chemical
• Well run study by Exxon/Mobil on DMC’s
teratogenic potential confirms it is virtually
identical to Methanol’s (NOEL 1,000 ppm)
Calif. OEHHA Conclusion
• OEHHA report concluded that doses levels
of DMC likely to be achieved by
environmental exposures to the public by
inhalation appears to have “relatively
minor” environmental health concerns
including no evidence of carcinogenicity
• Established interim acute and chronic REL,
where the acute REL is identical to MEK’s
and the chronic REL similar to Isopropanol’s
DMC Responsible Care
• Kowa American is committed to Responsible
Care® guidelines, we are upset with competitor’s
and enduser’s MSDS not referencing DMC’s
potential health hazards!
• We are urging all suppliers and users of DMC to:
Reference an industrial workplace REL of
100 ppm max. air over an 8 hour workday
Reference Methanol as DMC’s metabolite
Treat poisoning the same as methanol poisoning
BENZOTRIFLUORIDE - BTF
• Proposed VOC exempt solvent, EPA tabled
petition due to BTF’s revised MIR values
(2.8) in 2009 being higher than ethane (2.7).
• BTF is now allowed for aerosol coatings on
federal level (June 2012), and is still allowed
in Aerosol coatings in Calif. with a MIR
value or reactivity factor of .26 (2004 table).
• BTF’s similar solvency and evaporation rate
(BTF = 2.8 vs toluene = 2.0) to toluene
makes BTF a great replacement for toluene.
Flashpoint, E. rate, Boiling point
Evaporation Flashpoint
Rate
ºF
BuAc =1.0
Boiling
point ºC
DMC
3.22
63
90
PCBTF
.9
109*
139
Acetone
5.6
-4
56.5
<.005
269.6
240
Prop Carb
tBAc
2.8
40
98
BTF
2.8
54
102
MIR Reactivity Values (2009)
MIR gram basis MIR mole basis
DMC
0.055
4.95
Ethane
0.26
7.8
Acetone
0.35
20.3
Methyl Acetate
0.067
5.2
Prop Carbonate
0.27
27.56
Benzotrifluoride
0.28
40.91

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