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.




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)




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).




6

Outline







Outline

7

Challenges with today’s practices




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




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.




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

10

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) 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

11

Outline







Outline

12




13




Catalysts residues

Heat, shear, ..

P· + POH + H2O

POOH PO · + · OH

P-H

(Polymer)

PH

PH

UV light

POO·

P·

14




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•

15

Evolution towards NOR HALS




R

N

R

R

N

H

R

N

R O

R

N

R +

co-additives

to passivate

antagonistic

interactions

H+, S, Cl

Metals

16

Basicity of various hindered amines




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

17

Outline







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

18




19

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




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

20

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




21

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




22

IMPORTANT: While the descriptions, designs, data and information

contained herein are presented in good faith and believed to be accurate, it

is provided for your guidance only. Because many factors may affect

processing or application/use, we recommend that you make tests to

determine the suitability of a product for your particular purpose prior to

use. No Warranties of any kind, either expressed or implied, including

warranties of merchantability or fitness for a particular purpose, are made

regarding products described or designs, data or information set forth, or

that the products, designs, data or information may be used without

infringing the intellectual property rights of others. In no case shall the

descriptions, information, data or designs provided be considered a part of

our terms and conditions of sale. Further, you expressly understand and

agree that the descriptions, designs, data and information furnished by

BASF hereunder are given gratis and BASF assumes no obligation or

liability for the description, designs, data and information given or results

obtained, all such being given and accepted at your risk.

nor hals products for plasticulture_acs apr 2013.pdf

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