EVERSPRING MIDDLE EAST WLL The Long-Term Stabilization of Polyolefins … · 2018. 12. 5. · The...
Transcript of EVERSPRING MIDDLE EAST WLL The Long-Term Stabilization of Polyolefins … · 2018. 12. 5. · The...
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EVERSPRING
MIDDLE EAST WLL
The Long-Term Stabilization of Polyolefins
in Demanding Applications
Dr. Niall Marshall
Technical Manager, Everspring Middle East W.L.L.
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Everspring Middle East 2018
Overview
The polymer industry value chain
Antioxidants and Stabilizers:
o What are they?
o Why are they important?
Mature Industries and Innovation
Innovation in the use of Antioxidants in
Polyolefins
Conclusion
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Plastics Industry Value Chain
Monomer
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Plastics Industry Value Chain
Monomer
Polymer Producer
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Plastics Industry Value Chain
Monomer
Converter
Plastic Article
Polymer
Producer
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Plastics Industry Value Chain
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Antioxidants and Stabilizers
Added at low levels (0,1%) to polymers
to protect the polymer against degradationo most work either as radical scavengers or
hydroperoxide decomposers (“vitamins”)
o some light stabilizers absorb harmful UV light (“sun-
screen”)
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Antioxidant Chemistries
1
10
100
1 000
10 000
100 000
1 000 000
10 000 000
1.5 1.7 1.9 2.1 2.3 2.5 2.7 2.9 3.1 3.3 3.5
He
at A
gein
g R
esi
stan
ce [
ho
urs
]
Reciprocal Temperature [10-3/K]
Main Stabilizer Chemistries
Service Temperatures
ambienthighlow
moderatehigh
Processing Temperatures
Benzofuranones
Thiosynergists
Hindered phenols
Aromatic amines
Hindered amines
Hydroxyl amines
Phosphites &
phosphonites
EVERSTAB PS
EVERFOS
EVERSTAB FS
EVERSTAB
EVERSTAB LS
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EVERSPRING
Everspring Chemical Co. Ltd.
o established in 1988
o based in Taichung, Taiwan,
Everspring is one of the largest antioxidant producers in the world (including specialty antioxidants)
Supplies complete range of stabilizer chemistrieso Hindered phenolic antioxidants
o Phosphite stabilizers
o Hindered Amines
o Hydroxyl amines
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(Some) Phenolic Antioxidants
C(CH3)3
(CH3)3C
OH
(CH2)2 C OC18H37
O
HO (CH2)2 C NH
O
(CH2)3
2
HO (CH2)2 C
O
O (CH2)2
O CH2
2
HO
OH
OH
OH CH2
R=
N N
N
O
OO
R
R
R
CH2
OH
N N
N
O
OO
R R
RR=
OH (CH2)2
C O
O
CH2
C
4
OH OH
n
OH
SC8H
17
SC8H
17
OH
N
N
N
SC8H
17H
17C
8S
NH
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Plastics Industry Value Chain
Polymer Producer
Masterbatch Producer
Antioxidants
Processing Stabilizers
Light Stabilizers
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Plastics Industry Value Chain
Converter
Polymer Producer
Masterbatch Producer
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Antioxidant Requirements
Reactive
o React with the radicals, peroxides, etc. at a rate that
allows it to compete with the oxidation reactions
Chemically stable
o The antioxidant should not itself degrade during
processing and use
Compatible with the polymer
Safe
Regulatory compliant (including food contact use)
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Antioxidant Requirements
These antioxidants provide very economical
performance
o e.g., typically costs < $10,00 to stabilize 1 ton of polymer
the basic stabilization of polyolefins is usually much less than this,
but for demanding long term outdoor applications the cost will be
somewhat higher.
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Antioxidant Requirements
These antioxidants provide very economical
performance
o e.g., typically costs < $10,00 to stabilize 1 ton of polymer
High costs to commercialise new antioxidants Chemical registration (e.g., REACH, TSCA, DSL/NDSL, IECSC,
TCSI, etc.)
Regulatory approvals (e.g., Food Contact: FDA, EU, China,
Mercosur, etc.)
o Compliance costs depend on potential volumes (exposure)
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Antioxidant Industry
most polyolefins produced over the last 40 years
have been stabilized using one or more of the
following four antioxidants:
o EVERNOX 10-type
o EVERNOX 76-type
o EVERFOS 168-type
o TNPP (polyethylene only)
These antioxidants provide excellent stabilization
performance and have broad regulatory approvals
for the 164 million tons* polyolefins consumed
in 2017
*“Global Polyolefin Consumption Trends”, Nexant, SPE Polyolefins 2018
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Mature Market
A Mature Market is a market that has its
demand and supply in equilibrium
A mature market has:
o few new products being introduced
o increased competition
o decreased profitability
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Mature Market
Is an industry mature because there is no
innovation, or is there no innovation
because it is mature?
o Or is there, in fact, innovation even in mature
markets?
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“Innovation – something a
company can make money with...”
Dr. Hariolf Kottmann
CEO Clariant
President of CEFIC (European Chemical Industry Council)
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Innovation can include
Strategic Innovation
o M&A, divestments, backward/forward integration
Process Innovation
o Production or business processes
Market Innovation
o Solve [someone’s] problemsCustomer
Customer’s customer
Society
and they need to be willing (and able)
to pay for the solution
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Market Innovation Opportunities
Customer
o New markets
New polymers
Customer’s Customer
o New market needs
Processing conditions
Service conditions
Society
o New regulatory requirements
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New Polymers
catalyst and process advanced have resulted in
polyolefins with:
o different monomer distributions
o different MW and MWD
o different morphologies (heterophasic)
containing
o different catalyst residues (initiate degradation)
and with better mechanical properties, but
expected to maintain those properties for longer
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New Polymers
Which phases are more susceptible to
degradation? And which stabilisers are more
compatible with that phase?
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New Market Needs
more severe processing conditions
o higher shear rates
o higher temperatures
more demanding service conditions
o long service lifetimes
o outdoor exposure (sunlight / UV-light / rain)
o used in a harsh environment
exposed to water / acidic / basic / alkaline /
solvents (incl. fuel & chemicals)
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New Market Needs
Is the stabilizer system active enough at
higher processing temperatures? Are
sufficient levels of antioxidant being used?
Is there a need for a “booster”?
0,0
20,0
40,0
60,0
80,0
100,0
120,0
140,0
0 2 4 6 8 10 12 14 16 18
MFI
(g/
10
min
)
Time (minutes)
The Effect of Extrusion Temperature on MFI
200 degC 230 degC 260 degC 300 degC
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New Market Needs
Is the stabilizer system able to survive in
the environment where it is expected to
work? For decades?
0
20
40
60
80
100
120
0 5 10 15 20 25 30
Ret
ain
ed O
xid
atio
n In
du
ctio
n T
ime
[%]
Hot water aging time [weeks]
Retained OIT of samples after hot water ageing (85°C)
Reference
EVERSTAB ES-A
EVERSTAB ES-B
GRI-GM13 Specification
>55% after 3 months
72%
75%
35%
52% after 6 months
63% after 6 months
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New Market Needs
Is the stabilizer system able to protect the
molten polymer in air? For decades?
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New Regulatory Requirements
Regulation (EU) 10/2011 also included the term
NIAS (Non-Intentially Added Substances)
o A non-intentionally added substance is an impurity in
the substance used, or a reaction intermediate formed
during the production process or a decomposition or
reaction product.
Only “approved” products can be added
NIAS are not intentionally added and may not have been
approved
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NIAS Substances
any substance extracted from the polymer into a
food simulant which is (effectively):
o not included in the Union List
includes catalyst residues, reaction products, degradation
products, etc.
o present at > 10 ppb (if not CMR)
o has a molecular weight < 1000 Da
PP chain 23 monomer units (partly included in extractables)
and these substances need to undergo risk
assessment.
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For polymer producers:
A “Forest of Peaks”o Most peaks are not from the additives, they are from the polymer!
o Antioxidants reduce the amount of degradation (and some
antioxidants have very simple reaction products –easy to identify)
o Using the “right” antioxidants reduces the amount of NIAS from
degradation.
(Limit of Interest)
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Conclusion
For the polymer industry it is important that the
polymer performance window (processing, service
conditions and lifetime) continue to be increased,
and this requires improved stabilization
Although only a few stabilizers are widely used in
polyolefins there are many other stabilizers
commercialised and available – some of these (as
well as new combinations of stabilizers) will provide
the required improved stabilization…
…when used with a “first principles” understanding
of degradation and stabilization mechanisms
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Thank You
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EVERSPRING
EVERNOX - primary antioxidants (phenolic antioxidants)
EVERFOS - secondary antioxidants (phosphite antioxidants)
EVERNOX B - primary-secondary antioxidant blends (B-blends)
EVERNOX MD - Metal deactivators
EVERSTAB PS – thiosynergists
EVERSTAB FS – boosters (carbon-centered radical scavengers)
EVERSTAB ES – enhanced stabilization systems
EVERSTAB LS - hindered amine light stabilizers (HALS)
EVERSTAB - UV absorbers
EVERCLEAR - clarifiers
EVERPACK TOP - Tailored One-Packs
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Products*: Primary Antioxidants
Phenolic Antioxidants CAS Number
Evernox 10 General purpose providing excellent long term thermal stability in all polyolefins
6683-19-8
Evernox 76 General purpose with good compatibility in PE 2082-79-3
Evernox MD1024 High performance with metal (Cu) deactivator 32687-78-8
Evernox 1330 High performance with low extractability (pipes)
1709-70-2
Evernox 3114 High performance with low discoloration (fibres)
27676-62-6
Evernox 1520 High performance suitable for use in XLDPE (wire and cable) without affecting cross-linking
110553-27-0
* For a complete list contact Everspring Middle East
Primary antioxidants react with peroxy (ROO•) radicals to terminate the
oxidation process, providing long term stability to polymers as well as
protection during processing. Most primary antioxidants are sterically
hindered phenols.
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Products*: Secondary Antioxidants
Phosphite Antioxidants CAS Number
Everfos 168 General purpose, hydrolytically stable, providing good processing stability
31570-04-4
Everfos 626 High performance processing stabilizer 26741-53-7
Thioester Antioxidants CAS Number
Everstab PS800 Improved long term thermal stability when used with phenolic antioxidants in high temperature applications
123-28-4
Everstab PS802 Improved long term thermal stability when used with phenolic antioxidants in high temperature applications
693-36-7
* For a complete list contact Everspring Middle East
Secondary antioxidants react with hydroperoxides (ROOH) , preventing the
hydroperoxides from decomposing to form peroxy radicals. Secondary
peroxides provide processing stability to polymers and are also called
“processing stabilizers”. Most secondary antioxidants are phosphites or
phosphonites although thioesters or thioethers are also used in certain
applications.
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Products*: Antioxidant Blends
Phenol-Phosphite Antioxidant Blends
Evernox B110 1:1 Evernox 10: Everfos 168 “B225”
Evernox B210 1:2 Evernox 10: Everfos 168 “B215”
Evernox B310 1:3 Evernox 10: Everfos 168 “B220”
Evernox B410 1:4 Evernox 10: Everfos 168 “B561”
Evernox B201 1:2 Evernox 76: Everfos 168 “B921”
Evernox B401 1:4 Evernox 10: Everfos 168 “B900”
* For a complete list contact Everspring Middle East
It is well known that blends of high performance hindered phenolic
antioxidants used together with phosphites act synergistically to
provide improved polymer stability.
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Products*: Light Stabilizers
Hindered Amine Light Stabilizers CAS Number
Everstab LS 622 General purpose low molecular weight tertiary-amine HALS for low color applications
70198-29-7
Everstab LS 944 General purpose high molecular weight secondary- amine HALS
71878-19-8
Everstab LS 770 High performance monomeric secondary-amine HALS 52829-07-9
Everstab LS 119 High performance high molecular weight tertiary-amine HALS providing good long term stability
106990-43-6
Hindered Amine Light Stabilizer Blends
Everstab LS 783 1:1 Everstab LS 622: Everstab LS 944
* For a complete list contact Everspring Middle East
Hindered amine light stabilizers (HALS) react with the radicals
formed by high energy ultraviolet (UV) light and terminate the
oxidation process. In addition to providing light stability HALS also
improve the long term thermal stability of polymers.
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Products*: Light Stabilizers
Ultraviolet Absorbers (UVA) CAS Number
Everstab 326 General purpose benzotriazole UVA with broad food contact approvals
3896-11-5
Everstab 327 General purpose benzotriazole UVA 3864-99-1
Everstab 328 General purpose benzotriazole UVA with good color 25973-55-1
Everstab 234 High performance benzotriazole UVA for high temperature applications (low volatility)
70321-86-7
Everstab 360 High performance benzotriazole UVA for high temperature applications
103597-45-1
Everstab 5411 High performance benzotriazole UVA 3147-75-9
Everstab P High performance benzotriazole UVA 2440-22-4
Everstab 531 General purpose benzophenone UVA with excellent compatability in PE
1843-05-6
* For a complete list contact Everspring Middle East
Ultraviolet (UV) absorbers stabilize polymers by absorbing the
harmful UV light preventing the formation of radicals.