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    Weatherable Rigid PVC - The Effect of Light and Thermal Stabilizers PDF

    Uploaded by

    Pamela Chacón

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    Weatherable Rigid PVC: The Effect of Light and Thermal Stabilizers GERALD CAPOCCI Additives Division Ciba-Geigy Corporation Ardsley, New York Rigid PVC compositions used in outdoor applications such as siding. profiles. windows, and soffit predominantly contain a tin mercaptide thermal stabilizer. It is well known that tin mercaptides impart outstanding thermal stability to vinyl compounds, however, it is also well known that they provide only marginal light stability. Mercaptides can be used in these applications primarily because they are combined with high levels of titanium dioxide. They are not well suited for dark colored PVC and compositions without titanium dioxide. These require a more weatherable thermal stabilizer, such as a tin carboxylate. In this paper, principles for formulating rigid weatherable vinyl will be discussed. The influence of thermal stabilizers and the interdependence of light stabilizers and thermal stabilizers on PVC photostability will be emphasized. Data will be presented showing how one can formulate weatherable dark brown and pastel PVC through the use of tin carboxylate thermal stabilizers, the appropriate light stabilizers, and pigments. Traditional approaches to achieving weatherability will be com- pared to what can be attained by capitalizing on the latest advances in stabiliza- tion technology. Finally, methods for reducing TiO, concentration will be shown. INTRODUCTION {gid PVC compositions used in outdoor appica- tions such as siding, window profiles, and soffit predominantly contain tin mercaptide thermal sta- bilizer and between eight and twelve parts of tta- nium dioxide, This combination ofan efficient ther- mal stabilizer and a good light scattering pigment allows most white and pastel colored PVC to be used ‘outdoors for many years. However. this traditional method of achieving good light stability isnot appro- priate for dari brown pigmented PVC or for compo- sitions containing reduced or low levels of titanium dioxide. These more demanding systems require new technical approaches to the maintenance of PVC photostability. In this paper, the influence of thermal stabilizers and the Importance of proper selection of thermal Stablizers and light stabilizers to achieve good ‘weatherability s discussed. (The discussion is limited to PVC homopolymers.) Data ts presented showing how one ean formulate weatherable dark brown and pastel PUC through the use ofa tin carboxylate ther- mal stabilizer, the appropriate ultraviolet (UV) light stabilizers, and lightfast pigments. Reported for the first time isthe efficacy of hind- ered amine light stabilizers (HALS) tn rigid PVC. Also ‘included is a method for reducing titanium dioxide concentrations in a pastel PVC while maintaining good weativerabity JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1969, VOL EXPERIMENTAL Samples discussed In this paper were produced from dry blends prepared using a high intensity ‘mixer, They were elther directly extrudedor compres- sion molded following two-roll-milling. Temperature profiles were those typically encountered in commer: cial systems. Yellowness Index was measured according to ‘ASTM D-1925. Delta E was measured according to the Hunteriab system with the spectral component included. Impact strength was obtained with a Dynatup In- strumented impact Tester equipped with a Nicolet Digital Oscilloscope and an IBM Personal Computer. ‘The impact tester was controlled by an in-house. developed computer program. ‘Accelerated weathering was run using an Atlas Blectrle, CI 65 Xenon Weatherometer equipped with borosilicate inner and outer filters, set at 0.95 w/m? ‘radiance, with continuous light and a 102 minute dry and 18 minute spray cycle. RESULTS AND DISCUSSION Effect of Thermal Stabiltzer To achieve good weatherability, PVC must be for- mulated and processed properly. One formulation variable which has a great influence on the photo- stability of a PVC compound is the choice of thermal 11, NO. 4 198 Gerata Capocet stabilizer. While tin mercaptides are known to be ‘excellent thermal stabilizers, they are also known to provide marginal fo poor light stability (1, 2). Thelr [Baftability for outdoor applications depends to agreat Gegree on being combined with high levels of ita hum dioxide oF other sultable light scattering pig- ‘ment, This performance dependence 1s illustrated in Table 1. Methyltin or butyltin mercaptides combined ‘with titanium dioxide are by far the most widely used thermal stabilizer/light stabilizer system in the US. Fight weatherable vinyl industry. Tin carboxylates. another class of thermal stabiliz~ cers, sacrifice some heat stabilizing efficiency relative ‘tomercaptides: however, they provide inherently bet- ter ighe stability (3), The better light stability of tin ‘carboxylates can be primarily attributed to their UV light absorption characteristics. Tin mereaptides are “simply much stronger chromophores than in carbox: ylates as illustrated In Fig. 1. The absorbed light {from 300-250 nm) triggers a rapid photochemical ‘change in tin mereaptides reeulting in aevere diacol ‘ration. This is shown in Table 2 Because of the relatively high processing temper atures of rigid vinyl, maleate free carboxylates are preferred since tin maleates are known to be lacry- fiators at elevated temperatures. This discussion tx limited to a maleate free tin carboxylate, Tin Carbox ‘late T, which is identified in the Appendix. ‘Barium/eadmium soaps are also known to impart. ‘good light stability to rigid vinyl compounds. They fire used widely in Europe and in some U.S. applica tons. Their performance is ilustrated in Table 3, However. bartum/eadmium based systems are also known to be moisture sensitive, while cadmism is lunder attack for environmental reasons. These (0, points will make It difficult for barfum/eadmium based products to become significant factors in the U.S. rigid vinyl industry. ‘The remaining discussion wil focus on a specific tun carboxylate. Tin Carboxylate T. and a butyitin mercaptide. Effect of Rheology ‘Tin carboxylates as a class possess thermal stabt- Wing and lubrieant properties that are unlike mer~ ‘able 1, Etteot on Titanium Dios on Tn Mercaptie- ‘Stabiizea Rigid PUC™Floraa Expomure Yellowness index is", ___itel__12Mos.__24 Won Cewawotoy 86 3-186 3 58 ite ot 3 58s ee 2 ety Irpact Moir Prseeos Ae Absorption Spectra of Organotins = te omoniter | Te oconae Fig, 1. Spectra ts from 1% solution in methylene chloride, ‘Table 2. Compareon of Photostabity of PYC Thermal ‘hacer Nance Wontheramever Expocure el e-o8]> eren-elo| captides. Thus, they cannot be substituted for a mer~ feaptide on a one for one basis in a typleal rigid composition. Reformulation is necessary. The Mew Formulation should be a rheological match of the old o ensure similar processing characterises, Reo! ogy matching can be accomplished through the ase of a torque rheometer Table 4 shows how the rheology of a typical butyl {un mercaptide thermal stabilizer was matched with ‘Tin Carboxylate T. To achieve similar fusion char~ acteristics and degradation times, It was necessary. 108 JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1989, VOL. 11, NO. 4 Weatherable Rigid PYC: The Effect of Light and Thermat Stabilizers to use higher levels of the Carboxylate T and lower levels of lubricant. Pastel PVE ‘Titanium dioxide ts not available in quantities suf- ficient to meet the vinyl industry's demand. Ths has Jed to higher prices and has prompted vinyl producers {© look for ways to reduce their TiO, consumption One way to achieve this geal is to substitute a more weatherable thermal stabilizer for the tin mereaptide Usually found in pastel PVC. Aa example of this Io contained in Table 5. The table shows that after 24 months of weathering in Florida, Tin Carboxylate T js more effective than the tin mercaptide in main- (Glning good color when the TiO concentrations are “Table 4 Rigid PVC: Rheology Comparison—Tin Mercaptide to "Tin Cavoonyate To camonvate Merci we wooo 050 ‘arma Stabizee 18 28. Ipact Mocter 30 eo (became o on (Caciom Stearate 40 < oment yo ‘Rhea Te Ta carboxylate Mercapsce

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