Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide
ORGANIC PEROXIDES ( Catalyst in UPR Industry) · Why Safety ? •Organic peroxides contain...
Transcript of ORGANIC PEROXIDES ( Catalyst in UPR Industry) · Why Safety ? •Organic peroxides contain...
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SAFETY, OUR FIRST PRIORITY!!
ORGANIC PEROXIDES ( Catalyst in UPR Industry)
Akzo Nobel India Ltd
Prasad Pujari
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Akzo Nobel
•Akzo Nobel: Global Fortune 500 Multinational company
•Leading industrial company in coatings, Paints and Chemicals
•Listed on Euronext Amsterdam stock exchange
•Chemicals Industry leader on the Dow Jones Sustainability
Indexes
•Revenues totaled around Euro 15 billion (90,000 Cr)
•Employs around 68,000 people subsidiaries in more than 80
countries
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Peroxides (Initiators/Catalyst/Hardner)
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Peroxide Safety
Why?See this formula
R - O - O - R’
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Why Safety ?
• Organic peroxides contain relatively weak 0 - 0 bond in
their molecule.
• Due to this peroxides are thermally unstable compounds
i.e. sensitive to heat and will decompose above certain
temperature.
• Decomposition leads to heat production
• If this heat cannot be transferred to environment then a
runaway reaction occurs and peroxide will explode
violently with or without combustion after some time.
• Hence strict temperature control is required for handling
and storing Organic Peroxides to prevent undesired
decomposition.
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Contents
• Risk of Organic
Peroxides
• Hazardous properties
Organic Peroxides
• General safety aspects
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Application (cure reaction):
peroxide + resin cure + heat
Pure formulation (transport, handling, storage,…)temperature
peroxide decomposition products + HEATcontamination
Risk
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Risk – decomposition events
Gas evolution(hours, days)
Smoke, boiling, foaming (minutes)
Thermal
explosion
Fire
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Hazardous properties organic peroxides
• Thermal stability
SADT
Contamination
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Thermal stability - SADT
SADT: Self Accelerating Decomposition
Temperature
The SADT is the lowest ambient
temperature at wich self-accelerating
decomposition (runaway) occurs with
a product in the packaging as used
for transport
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Thermal stability – Flash Point
Flash Point is the lowest product
temperture at which the product vapor / air
mixture can be ignited .
Vapor pressure of peroxides is in general
low . Flash point of OP is only meaningful
when it„s below SADT of peroxide
formulation.
Flash point of organic peroxides does not
give any indication about it„s stability or
decomposition effect.
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Time
Unstable
Quality loss
Gassing/bulging
Decomposition gases
Stable
SADT
Temperature
Emergency Temperature
Storage
RUNAWAY
Induction time
Thermal stability - Traffic light picture
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SADT OF Products
PRODUCT SADT (°C) Ts Max
(°C)
Ts Min
(°C)
TBPB (Trigonox C) 60 25 10
MEKP (Butanox M50) 60 25 -
CHP (Trigonox K80) 75 40 -30
AAP (Trigonox 44B) 60 30 -10
BPO (Perkadox BT-50) 50 25
Ts = recommended max. storage temperature related to quality
Tc = control temperature: max. transport temperature allowed
by the regulatory agencies, temperature related to safety
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Temperture criteria
SADT Control Tem
(Transport
Tem)
Emergency Tem
Over 35 Degree 10 degree
below SADT
5 degree below
SADT
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Contamination
Time
TemperatureRunaway
Contamination
reduces the SADT of
organic peroxides
Runaway
SADT
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Contamination
Notorious examples are :
• Accelerators (Co, Vn, …..)
• Metal salts
• Amines
• Acids and caustics
• Construction materials like iron, copper
• Organic liquids
• Resins/monomers
Especially ketone peroxides are
very sensitive for contamination
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Hazardous properties organic peroxides
• Explosive properties
Thermal explosion
• Burning behavior
Ignitability
Most peroxides are difficult to ignite
Burning rate
Once ignited, they may burn fiercely
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Transport classification
Organic
peroxide
classification
Hazard rating Max. container
size
Type A
Type B
Type C
Type D
Type E
Type F
Type G
Explosive
Very high
High
Medium
Low
Very low
No
Banned
25 kg
50 kg (max.)
50 kg
400 kg/450 l
IBC‟s/tanks
Unrestricted
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Burning rate
Trigonox C(TBPB) 8.1 kg/min.m2
Trigonox 21 7.2 kg/min.m2
Butanox M-50(MEKP) 5.3 kg/min.m2
Perkadox BT-50 (BPO) 1.7 kg/min.m2
Acetone 0.5 kg/min.m2
Ethanol 0.7 kg/min.m2
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Effect thermal explosion
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RISK
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Transport incident with organicperoxide
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General safety aspects
• General rules
• Personal protection
• Spillage
• Fire fighting
• Storage
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General rules
• Work clean
• Do not smoke
• Avoid: open fire, sunlight, heaters
• Never mix peroxides with accelerators or other substances
• Packeging material is non-pigmented PE
• Use for weighing and handling only materials which are
compatible with peroxides (SS 316, PE, PP, PTFE)
(Non-pigmented)
• Leave peroxides in their original containers and close the
packaging after use
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• FIFO
• Empty containers completely. Wash with water. Do not reuse
again.
• Minimize amount of peroxides in work area.
• Avoid pack tightly closed glass bottles or metal cans.
• Keep away from heat sources
• Work in well ventilated area & Seek assistance from supplier
SAFE HANDLING OF PEROXIDES
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Personal protection
• Protective clothing
• Safety shoes
• Gloves (neoprene or
synthetic rubber)
• Glasses
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Personal protection
Avoid:
Contact with the eyes
First aid:
Rinse immediately
with water, at least 15
minutes. Keep eye
lids open. – Doctor
MEKP is Aggresive
Eye wash fountain
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Personal protection
Avoid:
Contact with the skin
First aid:
Rinse immediately
with water and wash
with soap.
Clothing contamination
must be removed and
place in water.
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Personal protection
Avoid: Ingestion
First aid: Do not induce vomitting, drink
large amounts of water.
Avoid: Inhalation
First aid: Bring to fresh air.
Seek Medical attention
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Spillage
• Liquids: absorb in absorbent,
e.g. vermiculite and add water
• Solids: wet down with water,
mop up mechanically and add
water
• Pastes: mop up mechanically
and add water
• Do not use incompatible materials
such as rags, sawdust or paper
• Remove as organic peroxide waste
to a safe location
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Fire fighting
• Call the fire brigade
• Extinguish a small fire with Dry
Chemical powder or
carbondioxide and apply water to
prevent re-ignition
• Extinguish a big fire with large
amounts of water from a safe
distance (fire brigade) 25 mtr.
Always follow local rules
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Our Storage rooms
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Mobile Storage rooms
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Transportation for Quality & Safety
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Storage: quantities < 150 kg
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SAFE STORAGE
• Ensure proper air circulation
• Distance between two pallets > 10 cms
• Distance between pallet and wall > 15 cms
• Store in original carton/package only.
• Monitor correct storage temperature regularly.
• Log every hour
• Mark the store with organic peroxide label.
• Adequate standby power and refrigeration facilities
• Avoid direct sunlight and all heat sources.
• Do not store peroxides together with other chemicals
• Keep MSDS hard copy in storage room
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Storage: large quantities
7
• Temperature sensor
• Sprinkler
• Fire resistant wall and roof
• Grating
• Catch basin
• Door acting as venting panels
• Evaporator
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• Bulged / Warm Package.
• Smoke from Packages.
• Smell.
• Fire.
Indications of Emergency
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EMERGENCY PROCEDURE FOR BULGED/WARM PACKAGES
• Check temperature of cold storage If possible, check product
temperature
• Take the bulged/warm package(s) to safe, open place
• Open the packages - slowly and carefully
• Keep upwind
-Depute trained personnel only
-Consider evacuation
-Apply fine water spray
• Wear S.C.B.A., PVC gloves apron. Wear safety shoes.
• Allow the product to decompose under controlled conditions
• Inspect other packages in cold storage for rise of temperature
• Continue Vigilance
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Typical handling/safety aspects
TBPB (Trigonox C)
• solidifies below 10°C
MEKP –
• Do not add MEKP to Resin solutions at
temperature above 45 degree
• Never mix with acetone , accelerators
• Prolonged storage above 38 DC to avoid
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Thank you for your attention & ……Time to see Video
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Any
“BE SAFE AT ALL TIMES”