Compounding PVC with renewable materials

D. Martinz*1 and J. Quadros2

PVC compounding with renewable materials is reviewed, including raw materials production technology, market dynamics and technical aspects of the finished products compared with current solutions. PVC resins produced from renewable ethylene and plasticisers obtained from vegetable oils are described and evaluated. An overview of the market changes that have enabled the competitiveness of biobased materials is also considered, outlining the agricultural technology and challenges and the state of the art of chemical processes to obtain renewable components for PVC formulating. Options to formulate with renewable components are discussed on the basis of a review of the literature. It is concluded that a PVC compound formulated with renewable resin and plasticiser is not only viable, but represents a natural evolution towards a more sustainable PVC supply chain. As a sample calculation, 1 ton of a clear flexible vinyl formulation with 100 phr resin and 60 phr plasticiser would remove 2?3 tons of CO2 from the atmosphere.
Keywords: Renewable compound, Green PVC, Sustainable, Resin, Vegetable plasticiser, Bioethanol

Introduction
This paper intends to address the question of technical, environmental and commercial viability of a renewable PVC compound. In the past years, the scientic community has invested signicant amounts of time and resources to evaluate the impact of human activities on climate change and the environment. At the same time, crude prices have soared to high levels, similar to those observed during the great petroleum crisis of the decade of 1970.1 The recent rise of the petroleum prices can be explained by a series of market forces, such as political instability, increased demand and changes of the strategic positioning of major producers. The last 20 years have also seen a continuous evolution of agriculture technology, including the areas of soil enrichment through fertilisers, reduction of losses with improved agrochemicals and storage, yields with irrigation, and species through genetic selection and modication.2,3 After the rst petroleum crisis, many companies and governments concerned with raw material availability invested in the development of renewable, sustainable alternatives. The result of this movement was the creation of new markets, such as the ethanol fuel in Brazil. In this second wave of the search for renewable alternatives, motivated by high petroleum prices and environmental concerns, many other fronts have been opened to explore vegetables as energy and raw material
1 2

alternatives. The number of biobased products related patents issued has increased signicantly in the past years (Fig. 1).4 The technology to obtain petroleum substitutes from vegetable and animal sources is not new. It is, in many cases, older than the processes that use petroleum as raw material. What is new is that vegetable originated materials are becoming more and more competitive and relevant to the needs of the global society. As a consequence, the technology to extract useful materials from vegetables is improving signicantly, resulting in improved nal quality and productivity. To produce a renewable PVC compound, this paper will focus the analysis on two major formulation elements (resins and plasticisers), demonstrating the technology of production, commercial and environmental sustainability and the quality in the nal applications. The detailed evaluation of llers and other additives, due to time and space limitations, should be the object of a later study.

Green PVC
PVC polymerisation: generals
Two of the most important raw materials to obtain PVC intermediates are salt, which provides the chlorine source, and ethylene, the hydrocarbon source. Salt comes from the seas or mines and ethylene is obtained from oil or natural gas. Chlorine coming from salt electrolysis is reacted with ethylene in order to produce 1,2-dichloroethane (DCE). DCE is then pyrolysed to split into vinyl chloride (VCM) and hydrogen chloride (HCl), which are separated afterwards via distillation columns. VCM is fed into reactors to be converted into PVC and HCl is sent to the oxychlorination unit, where it is combined with oxygen and ethylene to obtain extra

Solvay Indupa do Brasil Ltda, Rua Urussui, 300, Sao Paulo, SP 04542 903, Brazil Nexoleum Bioderivados Ltda, Estrada do Capuava, 1650, #2, Cotia, SP 06713-630, Brazil *Corresponding author, email daniel.martinz@solvay.com

2008 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 14 March 2008; accepted 28 May 2008 DOI 10.1179/174328908X362917

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1 Historical evolution of biobased product patents

dichloroethane, which is fed into the pyrolysis unit. The whole process is illustrated in Fig. 2.

From sugar and salt to PVC

PVC is known to be a polymer consisting of 43% hydrocarbons and 57% chlorine. This characteristic gives a natural advantage when it comes to fossil fuels supply, mainly ethylene. With the increasing prices of oil, alternative routes to produce ethylene became more and more attractive. One of them is the so called bioethylene route or green route, i.e. the generation of ethylene from ethanol coming from sugar cane. The process itself consists in dehydrating ethanol obtained from fermented and distilled sugarcane juice (Fig. 3). Ethanol is evaporated, superheated and fed into a catalytic reactor to break into ethylene and water. Water is eliminated in a quench column and ethylene in then compressed and dried via molecular sieve beds. A further distillation is necessary in order to comply with the specications for 1,2-dichloroethane production (Fig. 3). The production yield is 1 ton of ethylene for each 1?9 ton of ethanol consumed. This bioethylene is then pumped into the reactor to combine with chlorine, and the process follows as in Fig. 2.

2 PVC manufacturing process (adapted from Nass and Heiberger: Encyclopedia of PVC, 2nd edn)

and will prevent the emission of 300 kt/year of CO2 into the atmosphere, generating carbon credits. The nal resins, produced from ethanol, shall present no difference when compared to the oil based resins, since the specications of the raw materials (ethylene, chlorine) are exactly the same in both cases. This quality similarity has been widely veried in the past, from previous productions of ethanol based PVC by Solvay from 1962 to 1982.

Renewable plasticisers
Some well known renewable plasticisers, such as epoxidised soybean oil and epoxidised linseed oil, have been present for more than 50 years in exible PVC formulations. Although not considered to be primary plasticisers, these two materials are well known for improving the weathering and thermal stability of the nal compound, since the synergy with metallic salt thermal stabilisers (especially Ba/Ca/Zn) greatly improves the protection of PVC against degradation in high temperature9 and ultraviolet (UV) exposure.10 The main concern with these materials was their compatibility (exudation) and long term stability. Lutz and Wickson10 also indicated that the compatibility retention of epoxidised oils is inversely related to the iodine index. A reduction of the iodine index from 13 to 3 resulted in a useful life three times longer for the product formulated with epoxidized soybean oil (ESO). A further reduction of the iodine index to 1 resulted in another two times compatibility retention. The oxirane content is directly related to compatibility, since it indicates the concentration of molecules that have effectively been epoxidised. A low oxirane content may indicate that the reaction was incomplete or that oxirane rings started to open, forming less compatible hydroxyl groups. The conclusion, veried by weathering experiments, is that the efciency of the epoxidation process, maximising oxirane content and minimising iodine index, is vital to obtain a compatible, long lasting vegetable plasticiser. Another problem with the traditional epoxidised vegetable oils was the limitation of use, due to their higher molecular weight. Depending on the application and the components of the formulation, both ESO and epoxidised linseed oil (ELO) may be limited to a maximum percentage, to avoid the risk of exudation. Also, both materials are not sufcient to provide enough exibility for the formulators to achieve the desired physical and chemical properties of the compound. Traditional plasticisers, such as phthalates and adipates, would be necessary to provide additional degrees of freedom.

Brazilian ethanol
Brazil has a total arable surface of y360 million hectares (52% of its territory and 22% of the total arable area of the world),57 5?0 million8 of them indented for sugar cane crops. In other words, only a small portion of the arable Brazilian surface (y1?2%) is used for sugar cane plantations. Besides being renewable, ethanol is known to remove and x CO2 from the atmosphere.

Bioethanol based vinyl Brazilian project

In South America, Solvay Indupa is one of the leading PVC manufacturers, with one plant in Brazil (Santo Andre) and one in Argentina (Bahia Blanca), presenting a total capacity of 500 kt (thousand metric tons) of PVC/year. The Brazilian afliate has just announced an investment program to expand vinyl production, including the creation of an integrated plant to produce bioethylene with ethanol coming from sugar cane. The project will be nished in the rst half of 2010 and forecasts a plant with a total capacity of 60 kt/year of bioethylene, resulting in 125 kt/year of green PVC (at maximum capacity), i.e. PVC produced from an entirely sustainable source. It is expected a consumption of 120 kt of ethanol/year. This will be then the rst industrial facility in Americas using renewable resources for PVC production. This innovation is cost effective

3 Ethylene manufacturing process from ethanol

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6 Fusion temperatures22

4 Theories of compatibility to obtain useful renewable products, which can be appropriately tailored to each application and need of formulator, giving necessary degrees of freedom to formulate PVC compounds that will comply with demands of nal users: 2: DOA (dioctyl adipate); 6: BES (butyl epoxy stearate); 7: OES (octyl epoxy stearate); 18: DOP (dioctyl phthalate); 21: DIDP (diisodecyl phthalate); 30: ESO* (epoxidised soybean oil); 31: MES* (methyl epoxy soyate); 32: ACO* (acetylated castor oil) (*theoretical only)

In the past and recent years, researchers11,12 found that epoxidised esters obtained from the transesterication of various alcohols with vegetable oils were fully compatible with PVC resins, as much as well known phthalates such as DOP or DINP, with the added advantages of the improved UV resistance and higher thermal stability. Good compatibility has also been observed for the acetylation of castor oil.13 These materials have been extensively tested in the recent years and have been used commercially for many applications. The freedom of choosing the alcohols and the vegetable oils offers a huge range of possibilities (Fig. 4). Considering the Hildebrand parameters as a theoretical measure of compatibility, the curve below, extracted from Sears and Darby,14 compares some vegetable and traditional plasticisers. The phr of plasticiser absorbed is an indication of compatibility,

and the curve represents the theoretical value versus the actual results. The market dynamics for renewable plasticisers follows the recent trend where vegetable derived materials are becoming increasingly more competitive versus the traditional petroleum based products. The chart below (Fig. 5) demonstrates prices of crude oil over the years,15 DEHP (or DOP, dioctyl phthalate)16 and soybean oil.17 The cost of soybean oil have recently seen signicant increases, but even in this scenario, vegetable derived materials are presenting a cost advantage over petroleum derived materials. The long term competitiveness of vegetable derived plasticisers will depend greatly on the price differential between petroleum and oilseeds. These two markets are not directly related, since they depend on signicantly different drivers. It is the opinion of many analysts,1820 that the petroleum price should continue to rise through 2010, stabilise until 2013 and then rise again in the following years. In a recent evaluations regarding oilseeds markets,21 the expected trend is still upwards, but no conclusion was drawn regarding the maximum forecasted price nor the expected long term effects. It seems that for the oilseed prices, as renewable fuels increase, their participation in the overall demand, will be more and more inuenced by the energy demand, moving naturally to a dynamic similar to petroleum in the long term.

Renewable PVC compound

Based on the two main raw materials described previously, a renewable PVC compound can be produced, both in rigid or exible PVC. The renewable PVC resins, as explained earlier, will have exactly the same behaviour as traditional resins, since the building blocks, ethylene and chlorine, have exactly the same specications in both cases. Figures 6 and 7 and Table 1 show some of the

5 Price evolution charts

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8 Renewable concept: faster removal of CO2 from atmosphere of biobased materials when compared to fossil cycle25 7 Thermal stability (Metrastat, 175uC min21):23 HES5epoxy hexyl stearate, MES5methyl epoxy stearate

evaluations of currently commercial renewable plasticisers in comparison with traditional oil based materials. The tests of foam formation for spread coatings presented a signicant improvement of foam quality and reduction of kicker contents for the plastisol formulated with MES when compared with one formulated with DOP. Also, UV aging tests demonstrated signicant improvement of UV protection of MES when compared to DOP: the samples with DOP became brown and sticky, while the samples with MES presented yellowing and no stickiness. Printability was also improved with the use of MES, due to the higher surface tension of the compound, resulting in better ink adhesion.24 Table 1 is a compilation of various results comparing one commercially available and competitive vegetable plasticiser with DOP. The results indicate that the product presents signicant similarity to DOP and would be a valid replacement in many applications. Field tests have conrmed this perception and as of February/2008, MES presented a lower market price than DOP in Brazil, and would also be competitive in Europe, according to published market prices.16

materials, such photosynthesis happened many millions of years ago, and the sequestering effect is not relevant to the current needs. Sustainability, however, refers to a much broader perspective about the life cycle of a product, including the direct and indirect consequences to the environment and the human health of its means of production, its application and its disposal. In this sense, this paper will briey describe and analyse the sustainability of a renewable PVC compound.

Availability of raw materials

The substitution of petroleum fuels by renewable fuels such as ethanol and biodiesel are a controversial issue. The core of the debate lies around the effect of the increased demand for sugar cane and oilseeds on both food supply and deforestation. The benets of reduced CO2 emissions may be countered by the negative effects of reduced offer of land for food and increased deforestation. J. R. Moreira indicates26 that the technology is in place to have renewable sources, coupled with wind and solar power, replace the use of fossil fuels completely by year 2100, even considering the highest forecasted energy consumption. Such study does not take into account the social and economic difculties to carry on such change. It does not, either, consider the high probability of signicant improvements in the current technology of extracting valuable energy from renewable sources. In the past years, a signicant improvement in energy yields has been noted, which reinforces the idea that the volume of biofuels and bio raw materials extracted per hectare is still not at its optimum. The yield of ethanol per hectare28 have increased from 1?5 m3/ha in the 1970s to more than 7?0 m3/ha in Brazil between 1975 and 2005. Following the same trend, Figure 9 shows a clear improvement of soybean yield.

Sustainability
The term renewable in this paper refers to materials obtained from vegetable sources, such as soybean oil, castor oil, sugar cane, etc. Ethanol based PVC resin and renewable plasticisers are an obvious improvement in terms of reduction of green house gases in the atmosphere. Because of their vegetable origin, a certain quantity of CO2 is sequestered from the air through photosynthesis, resulting in a reduction of total CO2 in the atmosphere. In the case of petroleum based
Table 1 Performance comparison Compound properties,24 adjusted to same hardness Elongation, % Tensile strength, MPa Weight loss (144 h, 40uC), % Weight loss (72 h, 70uC), % Viscosity of plastisol (0 h, low shear, 1.4 s21), Pa s Viscosity of plastisol (48 h, low shear, 1.4 s21), Pa s Water extraction (75uC, 1% soapy water, 48 h), % Solvent extraction, (isoparaffin, 48 h), wt-% Butane extraction (48 h), wt-% Fish eyes, counts/dm2 Air entrapment measurement (volume of foam), cm3 Resin absorption (max. uptake at 74uC), min Low temperature (brittleness), uC

DOP 264 14.8 0.16 1.16 3.1 4.8 0.13 14.4 18.5 29 53 25 220

MES 357 16.2 0.51 3.67 3.5 5.7 1.82 3.36 9.7 21 65 8 223

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9 Soybean yield per acre27

Furthermore, the use of transgenic species, which would be less controversial for fuel sources, is still not fully developed. Also, some new technologies that could signicantly change the bases for renewable sources are in early stages of development. Among those, it is important to mention the extraction of ethanol from pulp of any origin and the extraction of useful oils and ethanol from algae. Considering the short term, the scientic community is pursuing an equilibrium between the exploration of renewable sources to replace petroleum with other energy sources, to properly address the global warming challenge. The issue of preventing renewables from affecting food supplies and deforestation must be continually controlled, through proper international policies, regulatory and non-governmental bodies, and the society. For the purpose of this paper, the volume of renewable raw materials for PVC would represent a fairly small portion of the total ethanol and oilseed production of the world. The total demand for PVC resins in the world is y33 000 kt/year,29 which would require an ethylene demand of y15 000 kt/year. This volume of ethylene would require a total of 28 000 kt/ year of ethanol, what would represent 2?5% of the Brazilian arable territory. The total demand for phthalates in the world is y5000 kt/year. Assuming, just for the exercise, that all this volume should be replaced by materials produced from soybeans, the whole plasticiser market would represent a share of 16% of the total soybean oil global production.8 Such volume would be covered by yield improvements alone, considering estimates from the Brazilian Agriculture Ministry that production per hectare can be enhanced 25% with improved agricultural technology.

planting, harvesting and processing. As mentioned before, the technology is evolving continually to more efcient systems. For the production of oilseed derivatives, the production of oils is currently based on solvent extraction, with reduced solvent losses. Non-solvent or ethanol based extraction is already available and in the early stages of feasibility studies. The subsequent processes, which can include hydrolysis, esterication, transesterication, epoxidation and hydrogenation, are all well known reactions commonly used in the food industry, to obtain various food additives or derivatives. These processes are also evolving rapidly as they become more relevant to the production of biofuels and raw materials for the chemical industry. The greatest concern for these processes is the generation of glycerin as a byproduct. Once again, there are several researchers30,31 investigating alternative uses for glycerin, such as composting for fertilisers or biogas generation, as its offer is increasing with the increasing demand for biodiesel.

Environmental impact and toxicology

The immediate benet of vegetable derived materials is the reduction of the CO2 in the atmosphere. Considering the current state of the art and the commercially available products, 1 ton of a fully renewable PVC compound for a clear vinyl calendered sheet, with 100 phr PVC resin, 60 phr vegetable plasticiser, 4 phr ESO and 1 phr Ca/Zn stabilizer, would represent a net reduction of 4?30 tons of CO2 from the atmosphere. The calculation is summarised below 100 kg green PVCz60 kg EMSz4 kg ESO z1 kg Ca=Zn stabiliser~165 kg compound 240 kg CO2 (Ref: 32)z141 kg CO2 (Ref: 33) z0z0~381 kg CO2 =(2:3 ton CO2 =ton compound) For the resins production from ethanol, the environmental impact of the nal product is exactly the same as with regular oil based resin, as they are exactly the same, chemically. Naturally, due to the recent nature of the renewable technology, toxicology and environmental evaluations are still considerably less extensive than the studies conducted for the major oil based plasticisers. However, some immediate benets have been noted, such as biodegradability and toxicology reduced impacts.34 Some products have been thoroughly evaluated, such as ESO or ELO, and some more recent materials are still being analysed. The initial results point to very encouraging perspectives, which are in line with the theoretical expectations, based on the chemical species of such materials.

Production processes
Several different processes have been developed to obtain ethanol from sugar cane and building block molecules from vegetable oils. The most prevalent process for ethanol is the extraction of the juice of sugar cane, fermentation and further distillation. Recent improvements eliminated the need for petroleum solvents in this process, and all the waste is reused: bagasse is burned to generate electricity and the vinasse is used as fertiliser for the sugar cane crops. To produce 1 L ethanol, 0?2 L are consumed in

REACH
All biobased materials must go through a series of analyses to comply with REACH, the European Community effort to ensure that all chemicals sold in Europe will be registered and have their physicochemical, toxicological and ecotoxicological properties well documented and evaluated. This will require that all these new chemicals have proper assessment of the associated risks and safety measures derived from the end uses and the supply chain.

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Conclusion
A completely renewable PVC compound, with the term renewable as dened previously in this paper, can be obtained for almost all applications with the materials that are currently commercially available and it is economically competitive when compared to petroleum alternatives. Naturally, with every new chemical, the evaluation and investigation of the recently introduced raw materials are still underway, but the initial results and the rapidly evolving agricultural and industrial technologies indicate that renewable PVC compounds are not only viable, but they arise as a natural evolution in the direction of a more sustainable PVC supply chain.

Acknowledgements
This paper is based on a contribution to PVC2008, the tenth International PVC Conference, organised by the Polymer Society of the Institute of Materials, Mineral and Mining in Brighton, UK, on 2224 April 2008.

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