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UV Stabilization of Organic Coatings

Mervin G. Wood, Ph.D.
Technical Expert
JPCL Webinar
November 11, 2015

Outline
 Ultraviolet Component of Light Sources
 Degradation and UV Light
 Ultraviolet Absorbers (UVA)
 Hindered Amine Light Stabilizers (HALS)
 Weathering Test Methods

 Conclusions

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Ultraviolet Component of Light Sources
 UV-C Region (up to 280 nm)
 Found only in outer space
 Filtered out by Earth’s atmosphere
 UV-B Region (280 to 315 nm)
 Responsible for polymer damage

 Absorbed by window glass to 290 nm
 UV-A Region (315 to 400 nm)
 Also responsible for polymer damage
 Dose is proportionally higher than C or B
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8 Irradiance (Watts/sq.2 UVB UVA 1 0.Ultraviolet Component of Light Sources ‒ Natural Sunlight* Miami. lower intensity (fewer photons in solar radiation) Longer  = Lower Energy per photon.8 0. higher total energy in sunlight *UV-B will increase with altitude 4 .6 1. higher intensity.6 0.4 Visible 0. Florida (June 17.4 UVC 1.2 0 250 270 290 310 330 350 Wavelength (nm) 370  390 410 430 450 Increasing Energy per photon Energy = h=hc/   Shorter  = Higher Energy per photon. meter) 1. 1983) 1.

Degradation and UV Light 5 .

 absorbed  reflected  scattered  transmitted  Absorbed energy can.  cause photolysis of polymers.. impurities  be transferred from one molecule to another  be emitted as heat or light 6 ...Degradation and UV Light Light Energy  Energy can be..

VCH..350 kJ/mol 360 -CH2-NR2 Amine 330 kJ/mol 400 -O-O- Peroxide 270 kJ/mol References: Morrison Boyd. Lehrbuch d. 1985 7 . Org. / sec.390 kJ/mol 340 R-CH2-CH3 Aliphatic 335 . Chemie. / tert.370 kJ/mol 350 -CR2-Cl aliphatic Chloride 330 .Degradation and UV Light Absorbed UV light can break bonds UV-B UV-A  / nm Bonding Type Bond Energy 230 -C-C- Aromatic 520 kJ/mol 286 R-O-H Alcohol 420 kJ/mol 290 R-CR2-H prim. H 410 / 395 / 385 kJ/mol 310 C-O-H Alcohol 385 kJ/mol 320 -C-O- Ether 365 . 3rd Ed.

Degradation and UV Light Absorbed UV light can break bonds 8 .

.Degradation and UV Light Mechanism of photo-oxidation DT.. h PO• + •OH PO• + POO• + H2O P• + P• P-P P• + POO• POOP (Peroxide bridge) PO• + PO• POOP (Peroxide bridge) P• + PO• POP (Ether bridge) 9 .) POO• POOH + P• PO• + PH POH + P• HO• + PH H2O + P• POOH 2 POOH DT. h • Initiation Polymer-P • Propagation / P• + O2 Branched chains • Auto catalytic Chain reaction • Termination / Recombination POO• + PH fast slow free radicals (P•. HOO•. HO•.. PO•. h DT.

Ultraviolet Absorbers (UVAs) 10 .

UV Absorbers UVAs – How they work  Prevent polymer degradation by absorbing light and converting to heat  Tautomeric mechanism allows long-term activity  Subject to Beer-Lambert Law – thickness dependent  Not very efficient in highly pigmented systems 11 .

.UVAs ‒ Degradation and UV Light R h .OH HALS work here 12 . ROO O2 R PH ROO . R* . + . ROOH + P h or D RO UV Absorbers work here .

UV Absorbers Benzotriazole UVA ‒ Mode of Action - R1 + R1 h D R2 “Enol form” (S0) R2 “Keto form” (S1) Energy dissipation Conversion of the absorbed UV light takes place in the excited singlet state 13 .

UV Absorbers Beer-Lambert Law  A = ebc  where A = absorbance  e = molar extinction coefficient  b = path length  c = concentration of UV absorber  Absorption (A) = -log T  T = Transmission Competitive absorption of harmful UV light 14 .

UV Absorbers  Governed by Beer-Lambert Law  Extinction Coefficient  UVA Concentration  Film Thickness  Range of Absorption  290 nm ‒ 400 nm  Properties  Compatibility  Regeneration  Photopermanence 15 .

UV Absorbers – Various Commercial Classes Oxanilide Benzotriazole Cyanoacrylate Benzophenone Triazine 16 .

50 UV-A UV-B VIS Absorbance c = 20 mg/liter in Toluene(Xylene). Oxalanilides absorbs efficiently only in UV-B  Benzotriazoles show best spectrum coverage 17 . path = 1cm 1.00 290 310 330 350 370 390 410 430 Wavelength / nm  Cyanoacrylates.00 Cyanacrylate Oxalanilide Benzophenone Benzotriazole 0.UV Absorbers ‒ UV absorbance spectra of UVA types 1.50 Triazine 0.

8% Triazine C 1.5% Benzotriazole B 1. Mw) 18 .6% 83.UV Absorbers ‒ Photopermanence 110 30mm Clear Coat with UVA + 1% N-Alkyl HALS on fused quartz plates (% UV-A determined at 345nm) UV-A retained / % 100 98.5% Benzotriazole A 60 50 0 500 1000 1500 2000 2500 Xe-WOM CAM 180 exposure / hrs  Photopermanence = f(UVA type.2% 90 89.5% Triazine B 1.2% 0.5% Triazine A 1.9% 80 Decreasing Photopermanence 70 76.2% 94.

5% N-Alkyl HALS 30 20 10 0 0 500 1000 1500 2000 2500 3000 3500 4000 Hours 19 .UVAs – Synergy with HALS Polyester Urethane Clearcoat/Bronze Metallic Basecoat. XeWOM = J2527 100 90 80 20 Deg Gloss 70 60 Unstabilized 50 2% UVA 1% N-Alkyl HALS 40 2% UVA/1.

20 .UV Absorbers ‒ Proper UV Absorber Choice  Substrate Sensitivity  UV wavelength sensitivity of resin binder or underlying resin  UV wavelength sensitivity of pigment  Sensitivity of color change (yellowing or pigment fading) for resulting article  Environmental Factors  Environmental conditions  Interior versus exterior  Duration of service (warranty)  Formulation Details  Solventborne. etc. waterborne. monocoat. 100% solids or UV cured  Basecoat/clearcoat.

Hindered Amine Light Stabilizers (HALS) 21 .

Hindered Amine Light Stabilizers Photostabilization with HALS  Regenerative  Effective in maintaining physical properties  Effective in pigmented as well as low Pigment to Binder (P/B) ratio formulations  Not thickness dependent 22 .

Hindered Amine Light Stabilizers How much effect can HALS have? 1% HALS X 10.000 Unstabilized X 1.000 2% HALS X 10.000 23 .000 Unstabilized Scanning electron micrographs of a white polyester polyurethane after 1300 hours QUVB (313 nm) HALS Function in Coatings  Gloss retention  Reduce cracking  Reduce chalking X 10.

ROOH + P h or D RO UV Absorbers work here . .HALS ‒ Degradation and UV Light R h .OH HALS work here 24 . ROO O2 R PH ROO . + . R* .

Hindered Amine Light Stabilizers Mechanism of Action – Modified Denisov Cycle R H R C O N Oxidation N R N O R O R' C O O or O O R' C O H or R' O + C R N R O C O O- + O H R' O O C R R R' H 25 .

1 A l k y l P i p e r i d i n e / AO h y b r i d 5.5 A l kox y P i p e r i d i n e 9.6 R1 = “Head Group” R2 = “Backbone” Activity Basicity Compatibility Solubility/Compatibility Equivalent Weight Basicity 26 .Hindered Amine Light Stabilizers HALS Basicity Piperidine pKb 5.0 Alkyl Piperidine 5.

HALS – Weathering Performance of HALS Type HSTSA Clearcoat/Silver Metallic Basecoat. Weathering = South FL 100 90 80 20 Deg Gloss 70 60 Unstabilized 50 2% UVA/1% N-Acyl HALS 2% UVA/1% N-Alkyl HALS 40 2% UVA/1% N-OR HALS 30 20 HSTSA = High Solids Thermoset Acrylic 10 0 0 10 20 30 40 50 60 70 Months 27 .

Weathering Test Methods Natural Weathering Accelerated Weathering         Florida Arizona Australia Other QUV-B (for high altitude simulation) Xenon with various light filters QUV-A (for terrestrial simulation) Many others Substrate Weathering Considerations     Environmental Factors Interior versus exterior Environmental conditions & pollutants Duration of service (warranty) 28 .

 Competitively absorb UV light to hinder radical initiation  Regenerate  Retard color change in low P/B formulations  Shield polymer from UV light and degradation  Exhibit synergism with HALS 29 ...Conclusions  UV Absorbers .

.  Terminate free radicals to prevent further chain reactions  Are effective in high pigmented as well as low P/B formulations  Regenerate  Are not thickness dependent  Reduce cracking and loss of tensile properties  Exhibit synergism with UVAs 30 .Conclusions Continued  Hindered Amine Light Stabilizers ..

Acknowledgements  Many thanks to Lori Boggs and Diane Langer for their contribution and support 31 .

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