NOR HALS Products for Plasticulture_ACS Apr 2013.pdf
description
Transcript of NOR HALS Products for Plasticulture_ACS Apr 2013.pdf
29-Mar-13 1
245th ACS National Meeting, Spring 2013
New Orleans, LA
N-O-R Hindered Amines for Improved Stabilization of
Plasticulture Films
April 7, 2013
Logan Hanner
2
Outline
Applications and Market Figures
Incumbent Systems and Challenges
Chemistry of Stabilization
NOR HALS as a Solution
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Outline
3
Plasticulture- what is it?
With the growing demand in agriculture during the last decades, growers have been looking for new technologies to enhance the techniques of cultivation
Plasticulture: portmanteau of plastics and agriculture
Any plastic material used to obtain better agronomic results, e.g. to facilitate crop cultivation, to enhance crop quality, to improve profitability or to reduce labor costs
Typically material encountered is polyethylene due to its low cost, physical properties, and ease of production
Applications may include greenhouse, mulch, and silage films, drip piping, hydroponics, and fibrous products.
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Applications and Market Figures
4
Market Demands
Efficiency: double farm output from today to 2050.
Energy: long term trend of price increase on seeds and inputs.
Environment: reduce the environmental impact of agriculture.
Source: IFAP (International Federation of Agricultural Producers)
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Applications and Market Figures
BASF Group – Ludwigshafen Germany
5
Market Figures
Acceptance of need for agricultural plastics has rapidly risen over the last 10-20 years, as CAGR has grown from 2.5% in the early 1990’s to approximately 5% in 2008.
Global demand for plasticulture now exceeds 4M tons annually.
Greenhouse and mulch films are about 2/3 of this total.
Asia leads the way in terms of sheer volume of plasticulture, although Europe trends towards higher performance films (multi-seasonal).
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Applications and Market Figures
6
Outline
Applications and Market Figures
Incumbent Systems and Challenges
Chemistry of Stabilization
NOR HALS as a Solution
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Outline
7
Challenges with today’s practices
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Incumbent Systems and Challenges
8
Traditional stabilizers in low performance ag films
Nothing in addition to antioxidants from resin supplier
Inexpensive UVAs, such as benzophenones
Secondary amines
Methylated HALS
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Incumbent Systems and Challenges
9
Increased use of agrochemicals
Elemental sulfur one of the oldest pesticides used by man.
Often burned in braziers to fumigate greenhouses.
Sulfur catalyzes degradation of film, rapidly destroying physical properties.
Also may generate sulfuric acid and interact with basic hindered amines to form ineffective salts.
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Incumbent Systems and Challenges
Percentage of analyzed film samples sorted by sulfur level (ppm).
About 20-30 film samples analyzed in 2008 from 2 years and 3 years greenhouse films
per country were taken in consideration.
Source: Product development Film & Fibre applications, (BASF Italy)
Percentage over 1,500 ppm of sulfur by markets
0%
10%
20%
30%
40%
50%
60%
70%
80%
Spai
nIta
ly
France
Gre
ece
Moro
cco
Egyp
t
Leban
on
Colo
mbia
Bra
zil
Turkey
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Interaction of agrochemicals with hindered amines
15 of 25 most commonly used agrochemicals showed deleterious effects on HALS light stabilizers
Sulfur based materials (yellow) showed increased reactivity with HALS than halogen-based compounds (orange).
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Incumbent Systems and Challenges
JJJ
(no reaction)
(L) L LL LLL
(strong reaction)
Dimethoate Prochloraz Metaflumizone Dithianione Metiram
Flufenoxuron Pyrimethanil Cymoxanil Thiuram
Alpha-
Cypermethrin
Iprodione Mancozeb Sulfur
Tebufenpyrad Dodine Metham Sodium
Kresoximmethyl Fenbutatin-
oxide
Metham Potassium
Boscalid Pyridaben
Pyraclostrobin
Metrafenone
Teflubenzuron
Dimethomorph
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Outline
Applications and Market Figures
Incumbent Systems and Challenges
Chemistry of Stabilization
NOR HALS as a Solution
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Outline
12
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Chemistry of Stabilization
13
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Chemistry of Stabilization
Catalysts residues
Heat, shear, ..
P· + POH + H2O
POOH PO · + · OH
P-H
(Polymer)
PH
PH
UV light
POO·
P·
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N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Chemistry of Stabilization
ROO• R=O + ROH
O2 light
R
N
H
R
N
O R
N
O•
R
H+, S, Cl, metals,..
NON ACTIVE
BY-PRODUCTS
R•
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Evolution towards NOR HALS
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Chemistry of Stabilization
R
N
R
R
N
H
R
N
R O
R
N
R +
co-additives
to passivate
antagonistic
interactions
H+, S, Cl
Metals
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Basicity of various hindered amines
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Chemistry of Stabilization
HALS HALS Type pKa
Low MW HALS NH 9.1
Low MW HALS NCH3 9.0
High MW Oligomeric HALS NH 9.7
Oligomeric HALS NR 6.8
High MW NOR HALS NOR 4.6
NOR HALS “Tinuvin XT” NOR 4.0
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Outline
Applications and Market Figures
Incumbent Systems and Challenges
Chemistry of Stabilization
NOR HALS as a Solution
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
Outline
Performance in LDPE Greenhouse Film
(Acid Treatment)
Polymer: 6-mil LDPE Greenhouse Film
Treatment: 24 Hours in 0.1N H2SO3 before Exposure
Exposure: Atlas Weather-Ometer Ci 65: 0.35W/m2 at 340nm, BPT 63°C, RH 50%, No Water Spay.
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0 500 1000 1500 2000 2500 3000 3500 4000 WOM Hours
Carb
on
yl A
bso
rpti
on
0.4% Secondary HALS
0.4% NOR HALS 0.4% Methylated HALS
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N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
NOR HALS as a Solution
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SKill 06/05: 25 µ LLDPE white Blown film (Dowlex NG 5056G) Time to 50% retained elongation
Accelerated weathering according to internal test (WOM exposure: 0.35W/m2 @ 340 nm – dry cycle) BASF Italy.
Mechanical test: elongation @ break according to ISO 527-3
pretreatment: H2SO3 0.1 N immersion for 24h at room temperature
NOR HALS
blend 300%
higher time
resistance
than
methylated
HALS alone
Time to 50% Retained Elongation
0 5000 10000 15000 20000
0.6% NOR HALS/
Me HALS blend
0.6% Methylated
HALS
T.Q.
hrs
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
NOR HALS as a Solution
KLys to 50% retained Elongation
0 100 200 300 400 500 600
0.6%Tinuvin NOR
0.6% Tinuvin XT
0.6% Methylated
KLys
t50 window
t50 iron
t50 pinewood
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Skill 02/01: 150 µ LDPE Blown film (Riblene FF29) Time to 50% retained elongation
Outdoor weathering @ Pontecchio Marconi experimental greenhouses (120Klys/y) BASF Italy.
Mechanical test: elongation @ break according to ISO 527-3
Treatments: Permethrine once a month and Metham sodium twice a year) Automatic spraying
Window= greenhouse cover part exposed to
chemical treatments and light
Iron= greenhouse cover part exposed to light
and in contact with galvanized iron frame
Pinewood= greenhouse cover part exposed to
light and in contact with wood frame
> 50% retained
elongation after
400 KLys
> 50% retained
elongation after
400 KLys
Improved
performance
on all typical
structural
support types
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
NOR HALS as a Solution
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Conclusions
Selection of ideal stabilizer hinges upon environmental conditions in the field (agrochemicals used, geography and corresponding heat and solar irradiance, crop type…)
Performance of hindered amine LS in conditions such as those found with harsh agrochemical is directly related to its pKa
Improvements to stabilization package can dramatically extend functional work life of greenhouse and mulch films, leading to significant boost to crop productivity
N-O-R Hindered Amines for Improved Stabilization
of Plasticulture Films
NOR HALS as a Solution
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