Patent Grant
9512292
This application is the U.S. national phase of International Application No. PCT/EP2011/062546 filed 21 Jul. 2011which designated the U.S. and claims priority to EP 10170791.7filed 26 Jul. 2010, the entire contents of each of which are hereby incorporated by reference.
This invention relates to a fuel part comprising a polymer composition and a process for preparing such fuel part.
Fuel parts are known and for example described in EP1609595. EP1609595 describes a multilayer container which can be extruded from extruders corresponding to the number of layers to be formed. However, this has the disadvantage that the method of production is complicated. EP1241229 describes a fuel resistant polyamide, which is used to prepare a part by injection molding. EP1241229 has the disadvantage that the parts obtained do not show the desired low fuel permeability in combination with good mechanical properties.
It is an object of the present invention to provide fuel parts in which the fuel permeation of the polymer composition in the fuel part is further reduced and in which the mechanical properties remain sufficient, especially the thickness distribution homogeneity when the fuel part is prepared by a blow-molding process.
It now has surprisingly been found that a fuel part, comprising a polymer composition comprising:
This has been exemplified in examples that are listed below.
The term “fuel” is here understood as comprising various mixtures of hydrocarbons used as fuel in internal combustion or high-compression engines. Thus, this term in particular encompasses fuel oil, diesel oil and all categories of petrol, as well as mixtures of hydrocarbons and alcohols, or the like. The fuel part according to the invention shows surprisingly low fuel permeability for ethanol containing fuels, also known as bio-fuels.
Fuel parts are here understood parts that can be in contact with fuel, such as fuel containers, fuel canisters, fuel caps, and fuel hoses. Fuel containers are herein understood means for containing fuel. Suitably, the container has one or more openings, suited for either separately or combined filling and/or releasing fuel.
The melt volume flow rate (MVR) of the polymer composition is measured according to ISO 1133 with a weight of 21.6 kg and at a certain temperature (hereafter abbreviated as Tmeasure). This measuring temperature is defined by the measure, melting temperature (abbreviated as Tm) of the polyamide A. For polyamides having a Tm of at most 260° C., Tmeasure=Tm+20° C. For polyamides having a Tm higher than 260° C., Tmeasure=Tm+10° C. Preferably, the MVR is at most 60 cm3/10 min at a weight of 21.6 kg and at a temperature of Tmeasure, more preferably the MVR is at most 50 cm3/10 min at a weight of 21.6 kg and at a temperature of Tmeasure A lower MVR is beneficial mechanical properties, especially when the fuel part is prepared by blow-molding, as then less sagging occurs and parison strength remains sufficient. Preferably, the MVR is at least 1 cm3/10 min at a weight of 21.6 kg and at a temperature of Tmeasure, as it is otherwise difficult to measure.
Where the polymer composition comprises more than one polyamide, Tmeasure is determined by the highest melting temperature of the polyamides.
Polyamide A
Polyamide A present in the fuel part comprising a polymer composition include all semi-crystalline polyamides.
“Semi-crystalline polyamide” is here understood to encompass polyamides having crystalline and amorphous regions. Suitable polyamides include aliphatic polyamides such as PA6, PA66, PA46, PA410, PA610, PA612, PA11, PA12, PA412 as well as blends thereof, but also semi-aromatic polyamides. Suitable semi-aromatic polyamides include terephthalic acid based polyamides like PA6T, PA9T, PA4T and PA6T6I, as well as PAMXD6 and PAMXDT, and copolyamides thereof, as well as blends thereof, as well as blends of aliphatic and semi-aromatic polyamides.
Preferably, polyamide A in the polymer composition is chosen from the group of PA6, PA66 or blends thereof, as this has the advantage that these polyamides are readily available and have god base fuel permeation level coupled with good level of ductility or resistance to impact.
Preferably, the ratio of terminal carboxy group concentration over terminal amino group concentration of the polyamide A is equal to 1 or higher. This ratio of terminal carboxy group concentration over terminal amino group concentration can be expressed as:
([terminal carboxy groups]/[terminal amino groups])≧1 form. I
whereby [terminal carboxy groups] is the concentration of terminal carboxy end groups in the polymer in meq/kg, and [terminal amino groups] is the concentration of terminal amino groups in the polymer in meq/kg. Terminal amino group concentration and terminal carboxy group concentration can be measured according to the method described in the examples. Preferably, the ratio of terminal carboxy group concentration over terminal amino group concentration of the polyamide A is higher than 1, more preferably at least 1.1 and even more preferred at least 1.2. This has the advantage that the thermal stability during melt processing is high.
Micro Talcum
Micro talcum present in the polymer composition preferably has a median diameter of less than 1 micrometer, more preferably less than 0.7 micrometer, even more preferred less than 0.6 micrometer. This has the advantage that the micro talcum is more effective in reducing the fuel permeation level than talcum particles with a higher median diameter. The particle size distribution of micro talcum is determined by a high speed image analyzer. This analyzer projects all particles in a limited sample into 2-dimensional images and measures the actual surface area of all captured separate particles. These surface area are subsequently recalculated into circles having the same surface area of which the diameter is calculated. The median value of the particle size distribution is then determined by known means.
Micro talcum may be present in the polymer composition in very low amounts, such as in an amount of at least 0.001 wt % with respect to the total amount of the polymer composition, preferably at least 0.01 wt %, more preferably at least 0.02 wt %, even more preferably at least 0.04 wt %, and still more preferably at least 0.05 wt %. Preferably, micro talcum may be present in the polymer composition in an amount of at most 1 wt % with respect to the total amount of the polymer composition, more preferably at most 0.5 wt %, even more preferred at most 0.2 wt % and even more preferably at most 0.1 wt %.
Amounts of micro talcum according to the invention have the advantage that the cold impact at −30° C. remains sufficient.
Polyamide B
Surprisingly, it has been shown that the further presence of a polyamide B being PA-410 in an amount of at least 0.1 wt % based on the total amount of the polymer composition in a fuel part according to the invention leads to even lower fuel permeability, as compared to fuel parts not comprising PA410. PA410 is here understood to be a polyamide containing monomer units of 1,4-diaminobutane and 1,10-decanedioic acid.
Preferably, PA-410 is present in the polymer composition in an amount of at least 0.2 wt % with respect to the total amount in the polymer composition. More preferably, the amount of PA-410 is at least 0.5 wt %, even more preferably the amount is at least 1 wt %.
Preferably, PA410 is present in an amount of at most 10 wt %.
Preferably, the polymer composition comprises a blend of PA6 and PA410 or PA66 and PA410. This has the advantage that the relative gain in fuel permeation reduction is big and the ductility of fuel part is good.
Other Additives
The fuel part according to the invention can optionally comprise other additives such as impact modifiers, fillers, rubbers, colorants, lubricants and branching agent.
Suitable fillers are mineral fillers such as clay, mica, talc, glass spheres. Reinforcing fibres are for example glass fibres. As reinforcing fibres the polyamide composition preferably comprises 5 to 60 wt % glass fibres, relative to the total amount of polymer composition, more preferably 10 to 45, and most preferably 15 to 40 wt % glass fibres. Suitable glass fibres generally have a diameter of 5-20 micron, preferably 8-15 micron, and are provided with a coating suitable for use in polyamide. An advantage of a polymer composition comprising glass fibres is its increased strength and stiffness, particularly also at higher temperatures, which allows use at temperatures up to close to the melting point of the polymer in a polymer composition.
Suitable impact modifiers are rubber-like polymers that not only contain apolar monomers such as olefins, but also polar or reactive monomers such as, among others, acrylates and epoxide, acid or anhydride containing monomers. Examples include a copolymer of ethylene with (meth)acrylic acid or an ethylene/propylene copolymer functionalized with anhydride groups. The advantage of impact modifiers is that they do not only improve the impact strength of the polymer composition but also contribute to an increase in viscosity.
Preferably the amount of impact modifiers is at least 1 wt % with respect to the total amount of the polymer composition, more preferably at least 5 wt %. This has the advantage that the impact strength is good.
Preferably, the amount of impact modifiers is at most 60 wt % with respect to the total amount of the polymer composition, more preferably at most 50 wt %. This has the advantage that the barrier properties remain sufficient. Preferably, the impact modifier is chosen from the group of maleic anhydride functionalized polyolefin.
As colorants for example carbon black or nigrosine can be employed. Preferably, the amount of extractables in a fuel part is low to avoid contamination of fuel lines and filters. Preferably, the fuel part is thus dispersant-free.
Process for Preparation of a Fuel Part
The invention also relates to a process for preparation of a fuel part. It has surprisingly been shown that the fuel part according to the invention can advantageously be prepared by the process of blow-molding or roto-molding.
Blow-molding is here understood to comprise at least the following steps:
The polymer composition used in step a) is the polymer composition as described in this description.
Roto-molding is here understood to comprise at least the following steps:
Fuel parts according to the invention, prepared by the process of blow-molding or roto-molding, exhibit a good thickness distribution homogeneity, combined with low fuel permeation. Another advantage is that the mechanical properties remain sufficient, such as the cold impact strength at −30° C. and less sagging occurs and parison strength remains sufficient.
The invention will now be elucidated by examples, without the wish to be limited hereto.
Methods
The fuel permeation rate (P) was measured by the weight loss method according to ASTM E96BW in which water has been replaced by ASTM fuel CE10 (composed of 10 vol. % ethanol and 90 vol. % of ASTM fuel C (50/50 wt % mixture of toluene and iso-octane)). The fuel permeation measurements were performed at 40° C. under dry conditions. The standard deviation in this method is between 5 and 10%.
Weight percentages are denoted with respect to the total weight of the polymer composition, unless stated otherwise.
Terminal Amino Group Concentration/Terminal Carboxy Group Concentration
The carboxyl end groups were potentiometrically determined in o-cresol by means of a titration with tetrabutyl ammonium hydroxide.
The amino end groups were potentiometrically determined in phenol by means of a titration with hydrochloric acid.
Cold Impact Data
Dynatup instrumented impact was performed using the guidelines of ASTM D 3763 and ISO 6603-2. Discs (2″×⅛″) were injection molded and tested −30° C. in a dry-as-molded state. The tup diameter was 0.5 inches with a lower clamp support diameter of 1.5 inches. The test speed was 6.8 ft/sec. At least five discs were tested. Discs of each material had been placed in a −30° C. freezer overnight. Test parts were transferred from the freezer to the test chamber one set at a time. The discs were tested after the chamber had equilibrated to the set temperature.
Melt Volume Flow Rate (MVR)
The MVR of the polymer composition was measured according to ISO 1133 with a weight of 21.6 kg and at a certain measuring temperature (hereafter abbreviated as Tmeasure). This measuring temperature is defined by the melting temperature (abbreviated as Tm) of the polyamide A. For polyamides having a Tm of at most 260° C., Tmeasure=Tm+20° C. For polyamides having a Tm higher than 260° C., Tmeasure=Tm+10° C.
Polyamides Used
Median diameter of 0.50 micrometer, 99% was less than 5 micrometer, 92% less than 2 micrometer and 75% less than 1 micrometer.
Impact Modifier
As impact modifier was used a maleic anhydride (MAH) grafted ethene copolymer.
Results
Table 1 clearly exemplifies that the combination of a MVR of at most 70 cm3/10 min and the presence of micro talcum results in a decreased fuel permeation (see Examples nr I and II), whereas an MVR of more than 70 cm3/10 min and no micro talcum present leads to higher fuel permeation (see Comparative Example C_1). In a composition where no micro talcum is present and a MVR of at most 70 cm3/10 min, the permeability is lower than in a composition with an MVR higher than 70 cm3/10 min (see C_2 compared with C_1), but still much higher than with compositions according to the invention (compare C_2 with Examples nr I and II).
Measurements on Fuel Tanks
Permeation measurements were performed on pre-soaked, sealed blow-molded tanks at 28° C. and atmospheric pressure, which were filled for at least 40 vol % of fuel CE10. The tanks were made from a polymer composition of 89 wt % PA6 with a ratio of terminal carboxy group concentration over terminal amino group concentration higher than 1, 9.75 wt % impact modifier and 0.08 wt % micro talcum. The MVR of the polymer composition was 37 cm3/10 min as measured at 275° C. at 21.6 kg. Various thicknesses were produced. The fuel permeation rate is presented in Table 2.
The results in Table 2 clearly show that a fuel part according to the invention shows a very low permeation rate.
Measurements on Blends
Fuel permeability was also measured on blends of polyamide-6 with polyamide-410. Also here a decrease in fuel permeability was observed upon presence of micro talcum.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10170791 | Jul 2010 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/062546 | 7/21/2011 | WO | 00 | 7/8/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/013569 | 2/2/2012 | WO | A |
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| 20130281599 A1 | Oct 2013 | US |
