Plasticizers transform the properties of PVC to create the attributes we need in each application. Most PVC applications have a life-span of 10 to 20 years and beyond.
Its long life-span makes PVC the perfect material for applications like building and construction. What is PVC? PVC has all the attributes needed to make it a widely used polymer. It is:. What are plasticizers? Most plasticizers are esters, that make PVC soft, flexible and easy to shape. ECPI is constantly feeding and receiving information to and from the entire value chain and other stakeholders including the media, regulators, scientists, and end consumers.
Journalists have been particularly appreciative when the industry is willing to talk and proactively provide valuable information for their work. We organize meetings, such as the annual Plasticisers Conference held in Brussels, which attracts dozens of companies and experts to discuss the latest scientific and regulatory developments in our sector. Our website at plasticisers. We are also active on Twitter ECPlasticisers and send out a quarterly newsletter.
Our conclusions indicate that our stakeholders are relatively familiar with the plasticizers industry in Europe and the work of the ECPI. They broadly have a positive impression of our importance, thanks also to the continuous collaboration between industry and other interest groups.
In general, we believe our interlocutors have become more aware of the work we do and our key messages. As ECPI, we pay close attention to scientific, industrial, and consumption trends. The European plasticizers industry is constantly adapting to the always-evolving legal requirements and consumer demand. In parallel, we can see that the use of plasticizers such as diisononyl cyclohexane-1,2-dicarboxylate DINCH and dioctyl terephthalate DOTP has also increased, reflecting our industry commitment to developing new and safe products through important investments in research and innovation.
Regulatory changes, of course, have a major impact on our industry. We must continue working together with regulators, the media, industries, and associations to ensure that plasticizers retain a key role in modern society.
In the future, we hope more companies will join forces under the ECPI to strengthen our advocacy impact and communication outreach.
This network enables the exchange of updated information about the regulatory status of plasticizers, best practices, and scientific findings. What fascinates me is the opportunity to make a scientific contribution in major regulatory decisions that could considerably affect the plasticizers market situation in Europe, and, hence, the jobs and prosperity of European citizens. Our association is also conducting a number of research projects with very reputable universities and institutes to increase knowledge about plasticizers and their possible effects and to provide consumers with high-performing and safe products.
Another interesting aspect is to see how close plasticizers are to people in their daily life, and how these substances can improve their lifestyle with myriad benefits to their health and the environment. This is why the misconceptions sometimes raised by the media or by inaccurate studies must be addressed by the ECPI by providing scientific data and reliable information about plasticizers and their safe use.
His work enabled the development of substances that are potentially active for cancer phototherapy. For scientific studies about plasticizers: News page on plasticisers. Geddes and J. It is hard to say how much change will take place in the next few years, but with the ever-changing ideas of science, breakthroughs could happen as soon as tomorrow. In the plasticizer industry, it could be years before we see any of the breakthroughs put into practice due to the testing and certification involved with plasticizers.
Plasticizers are a common additive that is used in various materials like PVC to make them more durable and more flexible. Plasticizers have been an important part of the materials industry for several years, and each year they get safer and more efficient than the year before. Many of the changes that happen with plasticizers are due to the rigorous testing. There is no doubt that plasticizers are valuable to many industries in the world today. What Are Plasticizers? What Are They?
What Are They Made From? What Are They Used For? What Are The Benefits? Drawn after data of ref. For a case where the plasticiser has a very high boiling point e. However, Ekelund et al. Smith et al. Surface blooming due to crystallisation and bleeding are effects of the deposition of migrated components on the surface. The surface of PVC floors tends to become sticky with time, which is caused by the formation of a plasticiser layer on the surface bleeding. Figure 1c also clearly shows the formation of a plasticiser film on the NBR surface in the evaporation-controlled mode.
By using sum frequency-generation vibrational spectroscopy, Zhang et al. Bellobono et al. Ljungberg et al. As shown in Table 1 , evaporation is, in general, the rate-limiting process for plasticiser migration at lower temperatures, whereas diffusion is the limiting process at higher temperatures.
Hence, the temperature-dependence is stronger for the evaporation process than for the diffusion process. Schematic of the Arrhenius plot for the kinetics rate parameter k controlled by evaporation below T c green line and by diffusion above T c blue line.
The red line and data points in regions A and B represent the overall migration rate of a plasticiser from a polymer.
The data points in region C represent the evaporation rates of plasticiser from the pure liquid. The plot is simplified and limited to the following special cases: 1 the diffusivity in the plot is taken as the average of the concentration-dependent diffusivity, 2 the system exists above the glass transition for all plasticiser concentrations, and 3 the temperature and plasticiser concentration effects on the diffusion and evaporation activation energies are not considered.
With the exception of temperature, other factors can affect the actual migration mode, especially when the ageing temperature is close to T c.
Royaux et al. Audouin and Verdu 30 observed that both the initial plasticiser concentration and the plasticiser size play important roles in determining the dominant mode. They observed that the evaporation-controlled mode dominates for large plasticisers and high initial plasticiser concentrations and consequently, that the diffusion-controlled mode dominates for small plasticisers and low initial plasticiser concentrations.
The authors also showed that the migration kinetics of both didecyl phthalate and dinonyl phthalate from PVC were controlled by evaporation when the concentration was higher than 20 wt. This agrees with the fact that the diffusivity is plasticiser concentration-dependent and decreases with the concentration Eq. In addition, a smaller concentration gradient at low plasticiser concentrations also contributes to the dominance of the diffusion-controlled mode. Their results indicate that in some cases, such as for the migration of plasticiser from samples with a high initial concentration of plasticiser, it is possible to observe both modes during ageing where the migration is at first controlled by diffusion and then switches to become controlled by evaporation when the concentration of plasticiser decreases beyond a critical level.
In addition, inorganic fillers e. As a result, the incorporation of fillers into commercial products of plasticised plastics is not so common or the filler is used in a small concentration. As an example, the outer layer of a fuel pipe made of plasticised polyamide 12 only contains 0. They explained that this was caused by a strong interaction between the plasticiser and carbon black.
The situation is different in rubbers where a large amount of carbon back is often used in combination with plasticiser. However, the effects of carbon black on the plasticiser diffusion have not been investigated separately. The type of plasticiser migration mode is traditionally determined by analysing the shape of the plasticiser desorption curve or the concentration profile within the sample.
The curves of the mass loss versus ageing time or the square root of ageing time are commonly obtained by intermittently measuring the mass loss as a function of time using an analytical balance or by measuring the remaining plasticiser concentration inside the sample.
The plasticiser concentration in polymers can be measured by thermogravimetry and infrared spectroscopy IR 30 directly, or by extracting plasticiser with solvents, followed by measuring the plasticiser concentration in the extracted solution with chromatography.
However, in the diffusion-controlled mode, the same measurement underestimates the average sample plasticiser concentration due to the existence of a concentration gradient towards the surface. In cases where it is not possible to monitor the plasticiser loss over time, the shape of the plasticiser concentration profile at a single ageing time can be used to reveal the migration mode.
Slicing is the most common method used to profile the plasticiser concentration. Additionally, in a recent study conducted by Adams et al. The expected lifetime of polymer products can be as long as several decades and for prediction purposes, the migration process needs to be accelerated by ageing samples at high temperatures.
The plasticiser loss can then be predicted by extrapolating the obtained data at high temperatures to service temperatures. Studies have shown that both the plasticiser evaporation and diffusion processes obey the Arrhenius law, which indicates that the Arrhenius law is valid for the extrapolation.
Hence, when considering large plasticiser concentrations and temperature intervals, this should not be ignored. Due to the existence of the two rate-dominating modes, accelerated ageing needs to follow the same migration mode as the actual service conditions. For instance, the highest accelerating temperature should be lower than T c for the actual case controlled by evaporation.
This requires the determination of the temperature regions for these two modes before selection of the accelerating temperatures.
Overlooking the existence of these two modes can lead to a false prediction. As shown in Fig. The plasticiser loss is typically controlled by the evaporation process at low temperatures, i. This makes the prediction easier since the evaporation process is independent of the glass transition temperature of the polymer and the plasticiser concentration within the polymer product, but it depends on the evaporation characteristics of the plasticiser.
For this case, a database of the evaporation rates of common plasticisers at different temperatures and their activation energies is useful for prediction purposes. However, this type of database covering various common plasticisers is currently not available. As mentioned above, the evaporation rate of a plasticiser from the polymer is similar within an order of magnitude to that from its liquid state when a plasticiser film forms on the surface.
The evaporation rate should be possible to estimate by using the evaporation rate data for the pure plasticiser directly. In this approach, the temperatures for accelerated testing can be greater than T c , as illustrated by the extrapolation of the data points in region C in Fig.
However, it is important that the high temperatures chosen for accelerated ageing should not cause any degradation of the plasticiser. Ekelund et al. In addition, other ageing processes, such as the oxidation and annealing of polymers, are also accelerated at high temperature.
In some cases, a plasticised-polymer product, such as a polyamide-based fuel pipe in a car, may experience high temperatures during service and diffusion-controlled migration. Plasticisers are increasingly used in a wide range of biopolymers to mainly improve their poor processability and make them more ductile and tougher. Studies have shown that the migration behaviour of plasticiser in biopolymers is often complex.
The cold crystallisation of biopolymers, such as PLA 38 , 54 , 55 , 56 and starch 57 , 58 , is accelerated in the presence of plasticisers, 59 which increases the crystallinity and then the plasticiser concentration in the amorphous region. This, in turn, affects the plasticiser diffusion properties during ageing. To avoid the deterioration of polymer materials caused by plasticiser loss, several approaches have been used to hinder plasticiser migration.
The most common way is to increase the molecular size of the plasticiser, which can be achieved by using polymeric plasticisers and oligomers, 64 , 65 and branched and star-shape plasticisers. However, plasticisers with a larger molecular size have a lower plasticising efficiency than most traditional plasticisers.
In addition, surface modifications, such as surface coatings and crosslinking, are commonly employed to suppress plasticiser migration.
In this paper, we discuss plasticiser losses from plastics and rubbers, losses which lead to inferior product properties, bleeding and eventual pollution of the surrounding environment.
The loss to the surrounding gas phase occurs through diffusion inside the material to the surface and through evaporation from the surface. The loss is either diffusion- or evaporation-controlled, where the former usually occurs at high temperatures and the latter at low temperatures. In the evaporation-controlled mode, a film of plasticiser is often formed at the surface, which is indicated by a linear loss with time, at least over a certain time period.
In addition to the temperature, the actual mode that dominates depends on several factors, including the plasticiser and polymer characteristics, product geometry and specific environment. The fact that the plasticiser diffusivity is plasticiser concentration-dependent can lead to a shift in the loss-mode from diffusion to evaporation control at otherwise constant conditions.
It is also shown here how it is possible to determine which mode limits the loss and the ways to extrapolate accelerated migration tests to service conditions. Warnings are also given that meaningful extrapolation and prediction of plasticiser migration requires consideration of several important factors.
We also highlight issues with new emerging systems with bio-based plasticisers in biopolymers. The data that support the findings modelling results of this study are available from the corresponding author upon reasonable request.
Rahman, M. The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges. Wypych, G. Handbook of Plasticizers.
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