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

29-Mar-13

N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Outline

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 Applications and Market Figures
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
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)

BASF Group Ludwigshafen Germany

N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Applications and Market Figures
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 1990s 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).
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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Outline

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 Incumbent Systems and Challenges
Challenges with todays practices

N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Incumbent Systems and Challenges
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
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.
80% 70% 60% 50% 40% 30% 20% 10% 0%

Percentage over 1,500 ppm of sulfur by markets

or oc co

yp t

Ita ly

Fr an ce

G re ec e

Le ba no

om bi

Br az il

Sp

Eg

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)

Co l

Tu

rk ey
9

ai n

N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Incumbent Systems and Challenges
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). JJJ
(no reaction)

(L)
Prochloraz Pyrimethanil Iprodione

L
Metaflumizone Cymoxanil Mancozeb

LL
Dithianione

LLL
(strong reaction)

Dimethoate Flufenoxuron AlphaCypermethrin

Metiram Thiuram Sulfur

Tebufenpyrad Kresoximmethyl

Dodine Fenbutatinoxide

Metham Sodium Metham Potassium

Boscalid Pyraclostrobin Metrafenone Teflubenzuron Dimethomorph

Pyridaben

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Outline

Outline

Applications and Market Figures

Incumbent Systems and Challenges Chemistry of Stabilization NOR HALS as a Solution

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Chemistry of Stabilization

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Chemistry of Stabilization

UV light
P-H (Polymer)
Catalysts residues Heat, shear, ..

POOH P

PO + OH PH

PH

POO

P + POH + H2O

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Chemistry of Stabilization
R
R N H R R

O2 light

N O

N O R

H+, S, Cl, metals,..

NON ACTIVE BY-PRODUCTS

R=O + ROH

ROO

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Chemistry of Stabilization
Evolution towards NOR HALS

H+, S, Cl

R N R

R N O

N H

N
R

co-additives to passivate antagonistic interactions

Metals
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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Chemistry of Stabilization
Basicity of various hindered amines
HALS HALS Type pKa

Low MW HALS
Low MW HALS High MW Oligomeric HALS

NH
NCH3 NH

9.1
9.0 9.7

Oligomeric HALS

NR

6.8

High MW NOR HALS

NOR HALS Tinuvin XT

NOR
NOR

4.6
4.0
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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films Outline

Outline

Applications and Market Figures

Incumbent Systems and Challenges Chemistry of Stabilization NOR HALS as a Solution

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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films NOR HALS as a Solution
Performance in LDPE Greenhouse Film (Acid Treatment)
0.4% Secondary HALS 0.4% Methylated HALS 0.4% NOR HALS

Carbonyl Absorption

0.2 0.18 0.16 0.14

0.12
0.1 0.08

0.06
0.04 0.02 0 0 500 1000 1500 2000 2500 WOM Hours 3000 3500 4000

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 63C, RH 50%, No Water Spay.
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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films NOR HALS as a Solution
NOR HALS blend 300% higher time resistance than methylated HALS alone
Time to 50% Retained Elongation

T.Q. 0.6% Methylated HALS 0.6% NOR HALS/ Me HALS blend

5000

10000
hrs

15000

20000

SKill 06/05: 25 LLDPE white Blown film (Dowlex NG 5056G) Time to 50% retained elongation Accelerated weathering according to internal test (WOM exposure: 0.35W/m 2 @ 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
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N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films NOR HALS as a Solution
Improved performance on all typical 0.6% Methylated structural support types
0.6% Tinuvin XT
> 50% retained elongation after 400 KLys

KLys to 50% retained Elongation

> 50% retained elongation after 400 KLys

0.6%Tinuvin NOR t50 window t50 iron t50 pinewood

100

200

300
KLys

400

500

600

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
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Skill 02/01: 150 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

N-O-R Hindered Amines for Improved Stabilization of Plasticulture Films NOR HALS as a Solution
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

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