FORMULATION ADJUSTMENTS FOR BIOBASED PLASTCISERS Authors: Jacyr Vianna de Quadros Jr. Marcos Antonio Teixeira de Mendonça Company: Nexoleum Bioderivados Ltda. ABSTRACT Following the global trend of the continued technological pursuit for sustainable solutions, renewable PVC plasticisers in compounds and plastisols have been consolidating their position in the market place. On top of the growing awareness and market relevance of “green” plastics and additives, replacement of traditional plasticisers due to regulatory impositions is promoting a significant growth of biobased materials. Biobased plasticisers have been especially successful in Brazil due to favourable market dynamics that enable formulators to replace phthalates and adipates with biobased materials while maintaining or even reducing compound costs. Drawing on extensive experience with actual industrial usage and test data accumulated over the past 5 years, the paper covers the review of paste PVC formulations with renewable plasticisers, focusing on the suggested adjustments to obtain desired performances of final articles. A series of issues and their corresponding solutions are presented, demonstrating how additives and resin combinations interact to match or improve performance over traditional plasticisers. Several performance areas are addressed such as: colour, rheology, stability, permanence, ageing, foam formation, expansion rate, etc. The paper also presents the areas where desired targets have not yet been met and could be subject for further formulation or even new resin/plasticisers development. The information includes data comparing traditional formulations of PVC plastisols and compounds with biobased alternatives, considering commercially available materials. The data and results reinforce one of the well known advantages of PVC over other resins: the ability to obtain desired properties through a proper and well balanced formulation, which creates the opportunity to play a leading role in the development of renewable sourced plastics. KEY WORDS Emulsion; Paste; PVC; formulation; biobased; renewable; vegetable; plasticisers; plastisols;

INTRODUCTION The increased regulatory pressure over traditional plasticisers has been motivating formulators to search with greater urgency for alternative materials. This pursuit has been particularly complicated by the fact that all existing alternatives do not present characteristics that would allow for a simple direct substitution of DOP (Di-octyl Phthalate) or DINP (Di-Isononyl Phthalate). The alternative plasticisers developed to date are similar, but present significant differences in performance that must be compensated with well studied combinations of additives and raw materials. This problem is the same for vegetable based products, also called bioderived, biobased or renewable plasticisers. As all other phthalate and adipates alternatives, these materials present singular characteristics that must be observed and properly adjusted in the formulation to reach desired specifications of the final products. Many controlled studies1 2 have been done to compare various renewable plasticisers, but these studies in many occasions are taken with precaution by the coated fabrics formulators since some industrial usage problems are not always well anticipated in controlled tests. These performance differences may be attributed to production behaviours that are not replicable or predictable in the laboratory scale. Brazil, due to its market dynamics, has been the stage for a significant growth of bioderived plasticisers, since the substitution of traditional products many times represents a reduction in formulation costs. This particular pricing situation promoted a broader use of renewable plasticisers, with a consequent much better understanding of the performance of these materials under industrial usage. The objective of this article is to present a compilation of paste PVC formulation solutions for coated fabrics obtained in the past five years of industrial scale sales and technical support in the substitution of traditional plasticisers, through both laboratory tests and real-life observations in the production facilities. EXPERIMENTAL METHODS AND MATERIALS For the laboratory tests, the data was obtained through controlled tests in the laboratory, for various formulations as shown in the tables below. Table 1: Laboratory tests and methods TEST METHOD Brookfield Viscosity ASTM D 1824-95 (2010) Gel Rate @ 80 °C. NEX-PE0104 Volatility @ 100 °C NEX-PE0103 Thermal Stability @ 210 °C NEX-PE0101 Shore A Hardness ASTM D 2240 (2010) Continuous flexing low temperature performance ABNT NBR 14.365:2006 In addition, a series of results and solutions observed in industrial usage are described, to document the technical issues that were raised in less controlled environments.

Table 2: Top, crystal clear formulations

T1 T2 T3 T4 T5 T6 T7

NORVIC P75 LMT 100 100 100 100 100 100 100

CaZn Stabiliser 2 2 2 2 2 2 2

DOP 57

DINP 57

DOA

57

ESBO 3 3 3

Octyl Epoxy Soyate 60

Methyl Epoxy Soyate

60

Nexo B5 (Complex epoxy esters) 60

Nexo MB50 (Complex epoxy esters)

60 Table 3: Viscosity adjustments for typical synthetic leather top formulations

A B C D E

NORVIC P75 LMT 70 90 100 70 70

SOLVIN 367 NK 30 10 - 30 30

DOP 55 30 - 30 - ESBO 5 - - - - Nexo B5 (Complex epoxy esters) - 30 60 - - Nexo MB50 (Complex epoxy esters) - - - 30 60

KZn Stabiliser 2 2 2 2 2 CaCO2 30 30 30 30 30 MB TiO2 / plasticiser (70/30) 8 8 8 8 8 ULTRAMAR Blue GP58 0.050 0.050 0.050 0.050 0.050

ULTRAMAR Violet V5 0.006 0.006 0.006 0.006 0.006 Table 4: Expanded layer formulations

X1 X2 X3 X4 X5 X6 X7

SOLVIN 367 NK 100 100 100 100 100 100 100 DOP 60

DINP

60

DOA 60

Octyl Epoxy Soyate

60

Methyl Epoxy Soyate 60

Nexo B5 (Complex epoxy esters)

60

Nexo MB50 (Complex epoxy esters) 60

KZn Stabiliser 2 2 2 2 2 2 2

CaCO2 20 20 20 20 20 20 20

Azodicarbonamide (diluted 1:1 in plasticiser) 6 6 6 6 6 6 6

Table 5: Viscosity adjustment formulations for a typical base of synthetic leather

O P Q R S

SOLVIN 367 NK 50 70 80 60 70

SOLVIN 370 HD 50 30 20 40 30 DOP 60 30 - 30 - ESBO 5 5 5 5 5 Nexo B5 (Complex epoxy esters) - 30 60 - - Nexo MB50 (Complex epoxy esters) - - - 30 60

KZn Stabiliser 2 2 2 2 2 CaCO2 40 40 40 40 40 Azodicarbonamide (diluted 1:1 in plasticiser) 4.5 4.5 4.5 4.5 4.5 MB TiO2 / plasticiser (70/30) 5 5 5 5 5 Obs.: Nexo B5 and Nexo MB50, patent US 8623947, are complex epoxy fatty esters, based on partial transesterification, acetylation and epoxidation of soybean oil. Table 6: Base and top formulation for low temperature flex test

PROD A PROD B PROD C PROD D

TA BA TB BB TC BC TD BD NORVIC P75 LMT 100 - 100 - 100 - 100 - SOLVIN 370 HD - 70 - 50 - 50 - 50 SOLVIN 367 NK - 30 - 50 - 50 - 50 DOP 20 40 - - - - - - DOA 40 20 40 20 30 10 20 - Nexo B5 (Complex epoxy esters) - - 25 40 35 50 45 60 CaZn Stabiliser 2 - 2 - 2 - 2 - ESBO 5 - - - - - - - Kicker KZn - 1.2 - 1.2 - 1.2 - 1.2 Azodicarbonamide 1:1 in plz - 4 - 4 - 4 - 4 CaCO3 - 30 - 30 - 30 - 30 MB TiO2 / plasticiser (70/30) 15 5 15 5 15 5 15 5 ULTRAMAR Blue GP58 0.5 - 0.5 - 0.5 - 0.5 - ULTRAMAR Violet V5 0.050 - 0.050 - 0.050 - 0.050 - Obs.: Product structure with 1.5 mm thickness, evaluated under low temperature, with the

following weights: TOP layer: 300 g/m2 BASE layer: 350 g/m2 TNT: 150 g/m2 TOTAL: 800 g/m2 Obs. 2: All paste formulations (Tables 2-6) were prepared with paddle mixer for 10 minutes,

rotation 500 rpm, @ 23°C

Rheology

As it can be seen from Figure 1, the viscosities of biobased materials are low after mixing, but ageing is more pronounced when compared to traditional plasticisers, except for the octyl soyate epoxidised.

Table 7: Hardness values, according to formulations from Tables 2 and 3 Formulation T1 T2 T3 T4 T5 T6 T7 A B C D E Shore A Hardness 72 76 72 75 68 68 73 76 74 74 77 78 Obs.: Shore A Hardness, 15 seconds, after 24h @ 23°C

Film Transparency

Formulations 1 to7 were evaluated visually for transparency. It was noted that all formulations presented good transparency, but some micro bubbles were noted for Methyl Epoxy Soyate (5), DOA (3) and Octyl Epoxy Soyate (4) formulations. This result might be related to deaeration efficiency under the test conditions. Light yellowing for vegetable materials was noted, when compared to phthalates or DOA, with Octyl Epoxy Soyate showing the least yellowing. DINP (2) presented slight presence of bubbles, and Nexo MB 50 (7) presented the best results.

Figure 1: Viscosity ageing of paste

Obs.: Brookfield Viscosity, ASTM D1824 - 95 (2010), 20 rpm, 23 °C

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Figure 2: Transparency Evaluations

Thermal Stability

As expected, thermal stability of epoxidised materials (4, 6, 7) is significantly superior to traditional plasticisers (1, 2, 3), due to the scavenging action of the oxirane ring recovering chlorine radicals from the resin matrix during degradation. This effect also suggests that it is possible to obtain similar thermal stability results for epoxy materials even with lower concentrations of stabiliser when compared to phthalate based formulations, which will be seen later.

Colour

Formulations from Table 3, with white pigment, were compared for colour. In comparison of DOP with Nexo B5 and Nexo MB50, a slight yellowing occurred in both vegetable based plasticisers, with Nexo MB50 a little less pronounced. Pictures were not able to demonstrate the differences, so they will not be shown.

Some correction might be necessary for the use of both products when used as the only plasticiser. The addition of Ultramar blue and violet has been successfully used in industrial applications to correct for these differences.

Gel rate

Gel rate tests were conducted in an 80°C temperature controlled bath, measured with Brookfield Viscometer spindle #6, at 20rpm rotation. Thermo-couple was installed 3mm from the spindle disk.

The gel rate of the biobased materials was faster than traditional plasticisers, except for the octyl epoxy soyate. This characteristic was expected, since epoxy materials are normally more efficient than traditional plasticisers. This is compatible with the viscosity ageing results obtained. For coated fabrics applications, this higher solvation may be beneficial, as it will result in less undesired impregnation of the textile reinforcements during the fusion in the oven. If these reinforcements

Figure 4: Gel Rate Evaluations

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Figure 3: Thermal Stability Tests, minutes @ 210°C, Table 2 formulations

get too impregnated, the final product has a tendency to become more rigid. It is important to note that this effect represents no concern regarding adhesion of the plastic layers to the textile, since that is achieved in a previous step and can be controlled by the pressure of the cylinder applied to the layers.

Viscosity Adjustments

Several formulations were prepared to demonstrate how it is possible to adjust viscosities and ageing while using renewable plasticisers. The results obtained are presented on Figure 5.

With relatively minor adjustments of PVC resin concentrations it was possible to obtain a viscosity profile quite similar to that obtained with DOP (Formulation A). Coated fabrics industries normally prepare their pastes 24 hours before processing. This time is necessary for colour adjustments, filtering and milling. Because of that, the industry seeks products with similar viscosities to the DOP standard at 24h ageing. From the chart it is possible to conclude that the formulations suggested presented satisfactory results.

It is important to note that these tests were conducted at 23°C. In the case of higher ambient temperatures, common in Brazil, especially in high speed mixers, this ageing effect is more pronounced and adjustments, as suggested, become absolutely necessary.

In addition to the resin combination adjustments, the use of viscosity reducers may be necessary. These additives are already widely used with traditional plasticisers

formulations. If the resin selection adjustment is correctly implemented, the use of viscosity reducers should be the same as already in regular usage. This effect was possible to be observed in real-life applications.

In the case of base coat typical expanded formulations, viscosity adjustments through the use of resin combination is even more necessary as these are pastes with a much more pronounced ageing effect than top base coats, as can be seen on Figure 6.

Figure 5: Viscosity ageing tests, top coat

Obs.: Brookfield Viscosity, ASTM D1824 - 95 (2010), 20 rpm, 23 °C

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Figure 6: Viscosity ageing tests, base coat

Obs.: Brookfield Viscosity, ASTM D1824 - 95 (2010), 20 rpm, 23 °C

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For formulation very loaded with calcium carbonate (>100 phr), the correction becomes even more complex and in many cases a final solution has not yet been achieved. For industrial applications, we have observed a limit of 80 phr for calcium carbonate loading. Beyond that value, it is possible to correct ageing with viscosity reducers, but in general there is a loss in the quality of the cell structure.

Expansion

As we can observe from Figure 7, X4 formulation presented a superior expansion rate over X1, X2 and X3. The quality of the expanded cells was similar for all formulations. The expansion rate was even better for X7, when compared to X2 and X6. Figure 8 shows all results at 90 and 150 seconds, for a direct comparison of all formulations. In general, the biobased plasticisers presented better results than traditional materials. The pictures shown on Figure 9 shows that cell quality is little affected when using bio-based materials, but there are some concerns at higher times (150 seconds), for the risk of over blow. FormulationX5 was not studied for expansion due to its high solvation and consequent quick ageing of the paste, making it unfeasible to prepare the expansion layer.

Figure 7: Comparative expansion rates @ 210°C of formulations from Table 4

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Figure 8: Expansion rates of Table 4 formulations

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Figure 9: Images of expanded layers, Table 4

Adjusted Formulations

Cell quality for all formulations was identical, no failure. The expansion rates were similar, with some advantage for the formulations made with pure biobased materials (Q and S). Renewable plasticisers presented slight yellowing when compared to DOP, and MB50 had less yellowing than B5. Formulations used 5phr of TiO2, which is typical for a base coat formulation that will carry a white top coat. According to industrial experience, colour differences with this pigment concentration presented no perceptible differences on the final product. Figure 11 shows the close-up pictures of the foam formation.

Figure 10: Expansion rates for adjusted formulations, Table 5

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Figure 11: Images of expanded layers, Table 5

INDUSTRIAL EXPERIENCE Exudation There have been reports of exudation from a few customers in the past years. It is important to separate each case categories to clarify the origin of the problem and propose the best solution. Low compatibility materials In many occasions exudations problems were observed due to the use of low compatibility materials that should not be considered primary plasticisers for PVC. To avoid these risks, it is important for the formulator to pay special attention to quality parameters of the material that will be used. Low compatibility materials may be used in formulations, but should be considered secondary plasticisers and great care should be taken to identify secure limits of concentration. Iodine index is a key indicator of double bonds contents, which may be the principal cause of incompatibility after extended times. Test have demonstrated that an iodine index reduction from 13 to 3 for epoxidised soybean oil tripled the compounds useful life, and a reduction to 1 further doubled that life time3. Cross-linking of the molecules at the double bonds in the presence of oxygen and light may be the key for the formation of less compatible molecules, resulting in exudation4. Simple yet fairly lengthy tests may be used to evaluate exudation. A commonly used test, in addition to the well known “loop test” (ASTM D3291), is the preparation of a black top coat with high gloss paper. Over time the surface is observed in parallel to a formulation with a standard formulation. Materials that present incompatibilities will normally present increased hazing of the surface over time. The test is conducted normally for a period of 90 days, separating samples with and without exposure to light. It is important to note that accelerated tests many times present results that are not representative of real-life ageing, for both accounts: negative or positive. Inadequate use of viscosity reducers Due to the high solvation nature of many epoxy plasticisers, plastisol paste ageing may prompt the use of higher quantities of viscosity reducers, causing exudation due to excessive hydrocarbons. In some cases, the use of low quality viscosity reducers, such as mineral spirits, aggravates the problem, as the higher molecular weight fractions are less volatile and are not properly eliminated during processing in the oven. Excessive quantities of plasticisers It important for the formulator to obtain information about the limits of use of the various available plasticisers. These limits should be presented by plasticisers producers, based on laboratory predictions and industrial performance. If limits of use are not clear, it is important to conduct compatibility tests as described above.

Odour Odour has in many occasions been a questioning for the use of renewable materials. Vegetable based epoxy esters have a characteristic odour that is unusual for operators. This difference caused complaints in some production facilities, but after a few weeks of continued use there was no issue as operators got accustomed to the new material, just like they’ve got used to traditional plasticisers when first started working in these facilities. For final products, the presence of other familiar odours, such as stabilisers and expansion additives, helps to reduce the differences between traditional and bioderived plasticisers. No reports of odour complaints have been noted for coated fabrics after plasticiser replacement. For high concentrations of plasticisers, such as in toy balls, odour differences have note by final users and masking scents were necessary to adjust the formulation. Special attention must be given to iodine index of epoxy plasticisers, as high values are indicative of high concentration of double bonds that may in turn cause a “rancid” smell after ageing of the final products. Foam quality If the formulation is not properly adjusted, there is a risk that foam quality be impacted. The size and shape of cells may be affected especially by the viscosity and fusion characteristics of the paste during expansion. As discussed previously, these effects can be properly adjusted with the use of resin combinations and a good understanding of the paste behaviour in various temperatures. Colour changes Tests with various pigments from yellow to black have shown that biobased materials present no visible changes in the colour of the final articles. For the white pigment, as well as crystal clear formulations, there is a slight yellowing that can be adjusted with the use of blue and/or violet pigments. Some pigments presented chemical interaction with epoxy materials, generating visible changes in final colour. For such pigments it is recommended to replace by other pigments with no such interactions or be aware of changes and formulate accordingly. Only copper phthalocyanine blue has been identified as having this characteristic until now. These were the pigments tested to date:

• Titanium Dioxide • Carmine HF 3C • Lead Chromate Yellow • Ultramar Blue and Violet • Copper phthalocyanine blue, alpha and beta crystals • Carbon Black

Increased speeds In theory, higher gel rates (as seen previously) should allow for higher speeds during processing. However, in industrial applications it is not trivial to take advantage of this characteristic, since the production train has other bottle necks that cannot be overcome and are not dependent of gel rate. A project reconfiguration would be necessary and that is not normally feasible. Viscosity changes Viscosity alterations are the main area of concern for the substitution of traditional plasticisers by biobased materials. These differences may be significant and, as seen previously, it is possible to adjust formulations properly to obtain desired results. These adjustments promote equalization of both on the immediate viscosity of the paste as well as after ageing. Special attention must be paid to the ambient temperature of operations. In practical applications, with temperatures easily reaching 40 °C, great viscosity changes happen in a short period, making viscosity adjustments absolutely necessary. Volatility Volatility is an inherent characteristic of the selected plasticiser. It is important to note that the volatility of the neat products (liquid) may not be directly proportional to that of the formulated final products, since the compatibility of the plasticiser plays a role in overall volatility after the PVC resin is cured. Figure 12 below demonstrates this effect.

To achieve desired volatility specifications, the formulator has to work with plasticiser selection. The advance of new biobased materials in past years has promoted the increase of available options for the formulation without the need to use traditional plasticisers.

Figure 12: Weight loss comparisons

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Pure products, liquid, bekers with 4 cm mouth diameter

Ventilated oven, 100 °C, 72H

Deareation Deaeration in the controlled tests were conducted in a Vacuum of -550 mmHg for 1 hour without agitation. Some biobased materials tend to present a slightly slower rate of deaeration. The tests presented above indicate that the deaeration of higher solvating materials, such as methyl and octyl epoxy soyate, was significantly slower than traditional plasticisers. Special attention must be given to ensure that the proper time and vacuum conditions are in effect to avoid bubbles in the final article. On the other hand, MB 50 presented good deaeration in spite of its higher fusion rate and efficiency. This effect has not yet been properly studied. Thermal and UV stability One of the best known effects of epoxy plasticisers is their thermal stability improvement in formulations, due to the co-stabilizing effect of the oxirane ring3, scavenging Chlorine radicals that are the main cause of PVC degradation. The UV protection follows the same logic, as described by Sears & Darby4. Accelerated UV tests have confirmed the literature theory, where formulations with epoxy plasticisers presented better UV resistance than phthalate based materials. In industrial usage, some formulators are managing to reduce stabiliser concentrations to reduce formulation costs without loss of thermal stability when compared to their original products. Figure 13 shows a study of laboratory results for reduced thermal stabiliser effects, demonstrating that it is possible to reduce formulation costs without performance loss. The stabilizing effect was similar at 5 minutes for Nexo B5 with 0.5 phr CaZn Stabilizer when compared to 3 minutes in the DOP formulation. It is important to point out that the DOP formulation had 5 phr of ESBO, as a co-stabilizer.

Figure 13: Thermal Stabiliser reduction

Resilience An effect that has been overlooked for biobased plasticisers is the increase of resilience. Materials with same hardness made from epoxy plasticisers will present higher tensile strength and higher elongation than phthalate based materials5. Figure 14 shows that effect for methyl epoxy soyate compared to DOP and DIBP.

Low temperature Low temperature flexibility is important for various plastisol applications, such as sports shoes. The key group of plasticisers to achieve desired speciDINA. Epoxy based materials present better low temperature performance than phthalates, allowing for formulators to obtain the desired characteristics by substituting phthalates and a portion of the adipates in the formulation. Table 6 indicates the formulations evaluated in a low temperature flexibility study, and the results were within specifications for all formulations, according to test method ABNT NBR 14.365:2006, which evaluates performance for 30 thousa10°C. Adhesion tests were also performed, with positive results for all formulations.

An effect that has been overlooked for biobased plasticisers is the increase of resilience. Materials with same hardness made from epoxy plasticisers will present higher tensile strength and higher elongation than phthalate based

Figure 14 shows that effect for methyl epoxy soyate

Low temperature flexibility is important for various plastisol applications, such as sports shoes. The key group of plasticisers to achieve desired specifications are the adipates, such as DOA or

Epoxy based materials present better low temperature performance than phthalates, allowing for formulators to obtain the desired characteristics by substituting phthalates and a portion of the

the formulation. Table 6 indicates the formulations evaluated in a low temperature flexibility study, and the results were within specifications for all formulations, according to test method ABNT NBR 14.365:2006, which evaluates performance for 30 thousa10°C. Adhesion tests were also performed, with positive results for all formulations.

Figure 14: Resilience effect of methyl epoxy

Low temperature flexibility is important for various plastisol applications, such as sports shoes. fications are the adipates, such as DOA or

Epoxy based materials present better low temperature performance than phthalates, allowing for formulators to obtain the desired characteristics by substituting phthalates and a portion of the

the formulation. Table 6 indicates the formulations evaluated in a low temperature flexibility study, and the results were within specifications for all formulations, according to test method ABNT NBR 14.365:2006, which evaluates performance for 30 thousand flex cycles at -10°C. Adhesion tests were also performed, with positive results for all formulations.

: Resilience effect of methyl epoxy soyate

CONCLUSIONS Alternative formulations to replace traditional plasticisers can be obtained with the use of vegetable (or renewable) based materials. The market conditions in Brazil allowed for a significant base of real life information on the industrial use of these products. These data has contributed to the growing reliance on the solutions proposed to adjust performance differences caused by the raw materials change. In addition, the development of new biobased plasticisers has added degrees of freedom for the formulator to achieve satisfactory results without resorting to the use of petroleum based traditional materials. The pursuit for solutions renews the importance of good professional formulators in the PVC industry. It also demonstrates the versatility of this resin, which has the opportunity to lead global achievement in renewable thermoplastics. The expected next steps are additional studies to properly address performance differences, development of new biobased plasticisers, and increased efforts in the research of specific resins and additives to optimise the performance of the new products.

LIST OF FIGURES Figure

Number Description Page

1 Viscosity ageing of paste 5 2 Transparency Evaluations 5 3 Thermal Stability Tests 6 4 Gel Rate Evaluations 6 5 Viscosity ageing tests, top coat 7 6 Viscosity ageing tests, base coat 7 7 Comparative expansion rates @ 210°C of formulations from Table 4 8 8 Expansion rates of Table 4 formulations 8 9 Images of expanded layers, Table 4 8 10 Expansion rates for adjusted formulations, Table 5 9 11 Images of expanded layers, Table 5 9 12 Weight loss comparisons 12 13 Thermal Stabiliser reduction 13 14 Resilience effect of methyl epoxy soyate 13

REFERENCES 1 MARTINZ, D. O., & MATTHYSEN, L. (2011). Evaluation of Processing Performance of Bio-Based Plasticisers in Paste PVC Application. PVC 2011 Conference

2 MADALENO, E. Estudo do Uso de Plastificantes de Fontes Renovável em Composições de PVC. Polímeros: Ciência e Tecnologia, vol. 19, nº 4, p. 263-270, 2009 3 WICKSON, E. J. , Handbook of PVC Formulating. Wiley, 1993 4 SEARS, J. K., & DARBY, J. R. (1982). The technology of plasticizers. New York, Wiley

5 KUESTER, F. E. ET AL. US Halogenated Polymers Containing Complex Epoxy Fatty Esters. Patent 3,281,382 – pg 19 lines 21-36