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High Performance Metal Stearates Thermal Stabilizers for Poly Vinyl Chloride

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High Performance Metal Stearates Thermal Stabilizers for Poly Vinyl Chloride International Journal of Petrochemical Science & Engineering Research Article Open Access High performance metal stearates thermal stabilizers for poly vinyl chloride Abstract Volume 4 Issue 4 - 2019 Low thermal stability of poly vinyl chloride (PVC) is one of the most serious problems 1 2 1 that facing its processing. In the present study some single and mixed metal stearate soaps Abd El-Ghaffar MA, Youssef EAM, Afify MF 1 were prepared, characterized and evaluated for their performance in enhancing and imparts Chemistry Department, Faculty of Science, Ain shams the thermal stability of PVC. Accordingly, calcium stearate, barium stearate, zinc stearate University Cairo, Egypt 2 and also the mixed metal stearate salt of calcium, zinc and barium were prepared by the Department of Polymers and Pigments, National Research Centre, Cairo, Egypt double decomposition of sodium stearate and single or mixed metal acetate solutions. The prepared metal stearates were characterized via spectroscopic analysis (FT-IR and XRD) Correspondence: Afify MF, Chemistry Department, Faculty in addition to micro analysis and thermal gravimetric analysis (TGA). The results showed of Science, Ain shams University Cairo, Egypt, Tel 01022232443, that the prepared metal stearates are good thermal stabilizers for PVC; also the thermal Email stability of the prepared (Ca/Ba/Zn) stearate was enhanced when melamine, ammonium poly phosphate, magnesium hydroxide and Ca/Zn phosphate are mixed with it. Received: September 6, 2019 | Published: September 30, 2019 Keywords: poly vinyl chloride, thermal stabilizer, metal stearates Abbreviations: PVC, Poly vinyl chloride; XRD, X Ray from partial PVC decomposition or substitution of labile sites of Diffraction; TGA, Thermo Gravimetric Analysis; FT IR, Fourier partially decomposed PVC macromolecules.5 Application of lead salts Transform Infra Red; Ca/Ba/Zn, Calcium, barium, zinc; Ba/Zn and organic tin stabilizers are limited due to their toxicity, even they Barium, zinc, Ca/Zn, Calcium, zinc; DOP, Dioctyl phathalate; ESBO, have high efficiency to stabilize PVC. The long-chain Carboxylate Epoxidized soya bean oil; min, Minute of metal ions are compounds of considerable commercial importance and are employed in various fields. For example, zinc soap is used Introduction as an ant moisture agent, a lubricant in polymers,12 or a dispersing agent in pigments. Mixed metal stearates predominate in the flexible PVC is an important thermoplastic material on account of its PVC applications in the United States and they find competition from versatility and low cost, however one major drawback of PVC is that lead based products in Europe for electrical wires and cable coatings.7 it decomposes at temperature lower than its processing temperature, In Europe mixed metal stabilizers are preferred for extruded rigid thermal degradation of PVC is the result of dehydrochlorination on 1,2 building profiles because they provide good weathering and physical exposure to heat which generates polyene sequences in polymer properties to PVC in this use, The most popular commercial products chains that may produce an undesirable color in material during 3,4 are combination including Ca/Zn, Ba/Ca/Zn and Ba/Zn, Calcium/zinc its molding and use, in the advanced stages of degradation PVC mixtures are used to stabilize PVC food packing, mineral water bottles losses mechanical, electrical and rheological properties as a result 7 5 and pharmaceutical containers thought the world Calcium/zinc has of chain scission and cross linking. During PVC processing, synergistic effect and present favorable stabilization; however Ca/Zn dehydrochlorination of PVC affects on mass loss and as a result of stabilizers have some disadvantages in long term stability due to its that color change to yellow, orange, red, brown and finally black zinc content. due to the number of conjugated bonds that formed.6 To overcome this problem, thermal stabilizers used to protect PVC from chemical Hence extra substance must be added so as to improve the degradation effects of heat, without the use of thermal stabilizers PVC efficiency of stabilization such as epoxidized soya bean oil13 could not be the widely used polymer.7 During the polymerization Melamine which is an organic base which contains 66% nitrogen by process the normal head to tail free radical reaction of vinyl chloride mass so it can capture hydrochloric acid and, if mixed with resins, deviates from the normal path and result in sites of lower chemical has fire retardant properties due to its release of nitrogen gas when stability or defect sites along some of the polymer chains, thermal burned or charred,14 Ammonium polyphosphate which is an inorganic stabilizer technology depends on prevention or repairing these defect salt of polyphosphoric acid and ammonia containing both chains and 7 sites. Thermal stabilizers include a wide variety of metallic soaps, possibly branching. Its chemical formula is [NH4 PO3] n and it can react commercial heat stabilizers in the market are actually synergetic with hydrochloric acid; ammonium polyphosphates decompose to mixtures of various compounds (mixed metal stearates and metal form ammonia and phosphoric acid so it act as fire retardant.15 Devrim hydroxides),6 Magnesium hydroxide can be used with metallic soaps Balkose et al.,16 studied the synergism of calcium and zinc soaps to enhance the thermal stability of PVC because it release weak Lewis on thermal stabilization of PVC using solvent casted films of PVC acid (magnesium chloride) when it react with hydrochloric acid. having commercial zinc and calcium soap in different proportions. 8 9 The metal soaps were characterized by X-ray diffraction and X-ray In general, the stabilizers are classified as lead salts, organic tin, ° 10 11 emission techniques, The films that were heated at 80 C for 4 hr for soap salts and rare earth stabilizers. Stabilizers play the role in the removal of the last traces of solvent methyl ethyl ketone were stability mainly through absorption of hydrochloric acid (HCl) released tested for thermal stability by heating at 160°C for 30 min. heated films Submit Manuscript | http://medcraveonline.com Int J Petrochem Sci Eng. 2019;4(4):162‒168. 162 ©2019 El-Ghaffar et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and build upon your work non-commercially. Copyright: High performance metal stearates thermal stabilizers for poly vinyl chloride ©2019 El-Ghaffar et al. 163 were characterized by infrared and ultraviolet-visible spectroscopy, mixed metal stabilizers were added in different ratios to PVC DSC and TGA methods the migration of zinc, calcium and hydrogen compound formulation that contain the following recipe. cations to water at 80°C was also studied. UV spectroscopic analysis Thermal Calcium and ion migration indicated synergism on PVC heat stability for 4:1 ESBO DOP PVC K70 Ca to Zinc soaps ratio stabilizer carbonate 3 or 5 2 50 60 100 Experimental work Other additives such as Magnesium hydroxide, melamine, Materials ammonium poly phosphate and Ca/Zn phosphate were added with i. Suspended Poly vinyl chloride with k-value 70 was obtained the prepared metal stearates in order to increase the stabilization ° from Egyptian company for petrochemicals (Alexandria) efficiency. All formulations were mixed on Bara bender at 150 C and 80 r.p.m., and then were prepared on a two roll mill of diameter 470 ii. Filler: Coated calcium carbonate was obtained from green Egypt mm and width 300 mm with speed of slow roll at 24 rev./min. A sheet Company for carbonates (10th of Ramadan) of 1 cm width and 20 cm length was prepared and tested in Metrastat static heat stability oven model IR-700 at 200°C for 2 hours in normal iii. Plasticizer: Dioctyl phthalate (DOP) was obtained from Egyptian air according to ASTM D-2115. Company for plasticizers and solvents (10th of Ramadan). iv. Co stabilizer: Epoxidized soya bean oil (ESBO) was obtained Characterization of the prepared single and mixed from hairma - china metal stearates v. Stabilizer: akropan 2611px (Ca/Zn stabilizer) was obtained from Micro analysis of carbon and hydrogen akdeniz kimya-turkey Micro analysis of carbon and hydrogen for prepared metal stearates vi. palmera Stearic acid was obtained from palm oleo - china were carried out on vario EI Elementar apparatus (Germany). The results are illustrated in Table 1. It is quite clear that the data of micro vii. Barium acetate was obtained from VEB LABORCHEM analysis given agree to a large extent with the calculated values for the APOLDA (Germany) proposed structures. viii. Calcium acetate was obtained from BDH chemicals LTD Table 1 Micro analysis of carbon and hydrogen (England) % % ix. Zinc acetate-2-hydrate was obtained from Arab lab company Molecular formula Hydrogen Carbon (U.A.E.) Theoretical Found Theoretical Found x. Magnesium hydroxide, Calcium/Zinc phosphate, Ammonium (C18H35O2)2Ca.2H2O 11.6 10.3 67.25 66.7 polyphosphate and Melamine were obtained from Sigma (C H O ) Ba.2H O 10.09 9 58.48 58.6 Aldrich (Germany) 18 35 2 2 2 (C H O ) Zn.2H O 11.16 8.8 64.7 64.5 Methods of preparation 18 35 2 2 2 (C18H35O2)2Ca/Ba/Zn 11.86 9.6 72.7 75.7 Double decomposition (precipitation) process was used for preparation of single and mixed metal stearate soaps.17,18 Determination of metal content by loss in ignition method ° Preparation of calcium, barium and zinc stearates The metal stearate salts were ignited at 1000 C for 1 hr in a muffle until the all organic content were lost then the percent of metal was These salts were prepared by two steps: calculated from the remained metal oxide (Table 2). i. Preparation of sodium stearate by neutralization reaction of Table 2 Metal content by loss in ignition method equimolar ratio of stearic acid and sodium hydroxide.
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