The present invention relates to a new method for the improvement of the barrier properties of ethylene homo- or copolymer against permeation of hydrocarbons. Such hydrocarbons are comprised in liquid fuels and mineral oil, whereby improved barrier properties are of predominant importance for the automotive industry, where plastic fuel tanks are comprised in automotive cars driven by combustion engines.

The invention also relates to articles of plastic and components for the transport and storage of liquid fuels such as plastic fuel tanks (PFT) for automotive vehicles driven by combustion engines, which are produced using ethylene homo- or copolymer compositions stabilized against permeation of hydrocarbons comprised in liquid fuels.

According to common practice in the art as described in DE-A-42 12 969, usually the inner surface of such articles of plastic is subjected to fluorination by means of any available fluorinating agents, mainly by elementary fluorine, however, such fluorination achieves a certain barrier level which is difficult to improve by further modifications in fluorination anyhow, at least not without increasing unduely the manufacturing costs.

It is the object of the present invention to provide a method to improve the barrier properties of a hollow body made of ethylene homo- or copolymer compositions against permeation of hydrocarbons comprised in liquid fuels, which hollow body is subjected on at least one surface to fluorination for producing articles of plastic and components for the storage and transport of liquid fuels. We have found surprisingly that this object is achieved according to the instant invention by a method subjecting at least one surface of a hollow body to fluorination, whereby such hollow body is made of an ethylene homo- or copolymer comprising at least one sterically hindered amine compound in an amount ranging from 100 to 10 000 ppm, calculated on total weight of the polymer.

Another solution of the problem is the preparation of articles of plastic and components for the storage and for the transport of liquid fuels, such as heating oil tanks or chemical storage or transport containers, especially plastic fuel containers for automotive cars driven by combustion engines, from ethylene homo- or copolymer compositions comprising at least one sterically hindered amine compound by blow molding technology and to subject at least one surface to fluorination. In a preferred embodiment of the invention, the inner surface of the blow molded hollow article of plastic is subjected to fluorination.

Another solution of the problem is the use of at least one sterically hindered amine compound to improve the barrier properties of ethylene homo- or copolymer compositions subjected to fluorination.

Suitable sterically hindered amine compounds for the ethylene homo- and copolymers are preferably the sterically hindered amines themselves, however, their N-hydroxy- or N-oxylderivatives may also be useful and other stabilizers may be added in addition thereto, such as sterically hindered amines including other secondary amines whose substitution on the carbons adjacent to the amine nitrogen is such that no single hydrogen remains at these positions. Preference is given to derivatives of 2,2,6,6- tetramethylpiperidine, substituted either at the 4-position or on the amine nitrogen, and to derivatives of quinoline and of diphenylamine.

Some preferred amine compounds in the aforementioned sense are: 2,2,6,6-tetramethylpiperidine, 2 _> 2,6,6-tetramethylpiperidine-4-ol ₎

2,2,6, 6-tetramethylpiperidine-4-one,

2,2,6, 6-tetramethylpiperidine-4-yl acetate,

2,2,6, 6-tetramethylpiperidine-4-yl 2-ethylhexanoate, 2,2,6, 6-tetramethylpiperidine-4-yl stearate,

2,2,6, 6-tetramethylpiperidine-4-yl benzoate,

2,2,6, 6-tetramethylpiperidine-4-yl 4-tert-butylbenzoate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) succinate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) adipate, Bis(2,2,6,6-tetramethylpiperidine-4-yl) n-butylmalonate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) phthalate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) isophthalate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) terephthalate,

Bis(2,2,6,6-tetramethylpiperidine-4-yl) hexahydroterephthalate, N, N' -bis(2,2,6,6-tetramethylpiperidine-4-yl)adipinamide,

N-(2,2 _I 6,6-tetramethylpiperidine-4-yl)caprolactam,

N-(2,2 _> 6,6-tetramethylpiperidine-4-yl)dodecylsuccinimide,

2,4,6-tris-[N-butyl-N-(2,2,6 _> 6-tetramethylpiperidine-4-yl)]-s-triazine,

4,4' -ethylenebis(2,2,6,6-tetramethylpiperazine-3-one) and tris(2,2,6,6- tetramethyl- 1- oxylpiperidine- 4- yl) phosphite and the N-hydroxy and N-oxyl derivatives thereof, as well.

Especially, the ethylene homo- or copolymer composition of the instant invention comprises as sterically hindered amine compound either Chimassorb ^® 944 or Tinuvin ^® 770 as sterically hindered amine compound. In a more preferred embodiment, however, the ethylene homo- or copolymer comprises a combination of these with other sterically hindered amine compound. In a most preferred embodiment it comprises the combination of Chimassorb 944 and Tinuvin 770 with each other.

The total amount of sterically hindered amine compound present as a combination of two different sterically hindered amine compounds in the polymer is defined as the sum of each single amount of each single stabilizer, whereby the ratio of the single amounts of the single stabilizers to each other ranges from 1 : 0,2 to 1 : 5, preferably from 1 : 0,5 to 1 : 2, based on weight- .

The sterically hindered amine compound Chimassorb 944 is thereby understood to have the following chemical formula:

addressed as: poly[[6-(1 ,1 ,3,3-tetramethylbutyl)amino]1 ,3,5-triazin-2,4- diylj^^.e.e-tetramethyW-piperidinyOiminopi .θ-hexandiyl^^.β.θ- tetramethyl-4-piperidinyl)imino]], whereby n is an integer ranging from 2 to 20.

The sterically hindered amine compound Tinuvin 770 has the following chemical composition:

addressed as: is-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate.

We have also found articles of plastic and components for the transport and/or storage of mineral oil or chemicals or liquid fuels comprising hydrocarbons having improved barrier properties, if they are produced using such polymers comprising sterically hindered amines either alone or in combination and subjected on at least one surface to fluorination. A preferred ethylene homo- or copolymer compositions stabilized by adding a combination of the two sterically hindered amines Chimasorb 944 and Tinuvin 770 in an amount of from 200 to 5000 ppm, more preferred from 400 to 3000 ppm, calculated on total weight of the stabilized polymer, is used for an optimum improvement in combination with fluorination.

The ethylene homo- or copolymer composition used in a preferred embodiment of the invention comprise the combination of sterically hindered amines as such or it comprises their N-hydroxy or N-oxyl derivatives.

The term ethylene homo- or copolymer composition is understood to address a polymer comprising ethylene as a main component which has been prepared by polymerization under low pressure conditions in the presence of a suitable polymerization catalyst. Common catalysts for the polymerization of olefins are titanium based Ziegler catalysts or chromium based Philips catalysts. These catalysts are used world wide for the manufacture of polymers in world scale production plants. Other suitable catalysts are zirconium based metallocene catalysts which habe been developed within the last twenty years and which are now described in many publications world wide.

As co-monomers for the ethylene, other homologue olefins are suitable comprising from 3 to 10 carbon atoms, such as 1-propene, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene and 1-decene. The co-monomers may be present during the polymerization of the ethylene in an amount of from 1 to 8 % by weight, preferably from 2 to 7 % by weight, calculated on total weight of the monomers present in the reaction mix. The polymerization takes place in a polymerization reactor, whereby different techniques are possible such as slurry polymerization in stirred vessels or in loop reactors or gas phase polymerization in stirred bed or fluidized bed reactors.

For use in the field of extrusion and blow molding, the polyethylene preferably has a melt flow rate MFR (190/21.6) of from 1 to 25 g/10 min, in particular from 2 to 20 g/10 min, and for use in the field of injection molding, an MFR (190/2.16) of from 0.1 to 100 g/10 min is preferred, in particular from 0.2 to 10 g/10 min.

Particularly suitable for use in accordance with the invention are ethylene homo- and copolymers having a density of from 0.930 to 0.970 g/cm ³ , in particular from 0.940 to 0.960 g/cm ³ , and, with particular advantage, the polymer employed is HDPE as normally used, for example, to produce PFTs.

The polyethylene normally includes additional substances for thermal and in-process stabilization. These substances, which may also be used in combination with the RME resistance stabilizers used in accordance with the invention, include sterically hindered phenols, which may also contain nitrogen and/or sulfur as heteroelements, lactones, which may also contain nitrogen and/or sulfur as heteroelements, organic esters of phosphorous acid (e.g. trialkyl phosphites), which may also contain nitrogen and/or sulfur as heteroelements, and alkali metal and alkaline earth metal stearates. Examples of stabilizers from the class of sterically hindered phenols are benzenepropanoic acid 3,5- bis (1 ,1- dimethylethyl)- 4- hydroxy- 2,2- bis[[3- [3,5- bis(1 ,1- dimethylethyl)- 4- hydroxyphenyl]-1-oxopropoxy]- methyl]- 1 ,3- propanediyl ester (IRGANOX 1010 from Ciba Additives GmbH), benzenepropanoic acid 3,5- bis(1 ,1- dimethylethyl)- 4- hydroxyloctadecyl ester (IRGANOX 1076 from Ciba Additives GmbH), 4- [[4,6- bis(octylthio)- 1 ,3,5- triazin- 2- yl]amino]- 2,6- bis(1 ,1- dimethylethyl)phenol (IRGANOX 565 from Ciba Additives GmbH), and N ₁ N' - hexamethylenebis(3,5- di- tert.butyl- 4- hydroxyhydrocinnam- amide) (IRGANOX 109 from Ciba Additives GmbH). Examples of stabilizers from the class of the lactones are benzofuran- 2- ones, such as 5,7- di- t- butyl- 3- (3,4- dimethylphenyl)- 3H- benzofuran- 2- one. Examples of stabilizers from the class of the organic phosphites are 2,4- bis(1 ,1- dimethylethyl)phenol phosphite (IRGANOX 16 from Ciba Additives GmbH) and phosphorous acid [1 ,1 ^* - biphenyl]-4,4' - diylbis- , -tetrakis[2,4- bis(1 ,1- dimethylethyl)phenyl] ester.

The incorporation of the stabilizers into the polymers can take place, for example, during the production of a granular base material or during the melting operation in preparation for shaping, which can take place, for example, by extrusion, injection molding or blow molding.

The ethylene homo- or copolymer compositions used in accordance with the instant invention are outstandingly suited to the production of articles of plastic and components for the transport and storage of liquid fuels comprising hydrocarbons, especially also for liquid fuels comprising biodiesel in some amounts, as they have improved barrier properties against permeation of hydrocarbons, if fluorinated, in comparison with other ethylene homo- or copolymers not comprising the sterically hindered amine compounds of this invention, if fluorinated as well, y articles of plastic and components in this context are meant all the plastics parts which are exposed to the liquid fuels for a prolonged period, especially heating oil tanks, chemical storage or transport containers, plastic fuel tanks, but also parts such as pipes and feedlines, bottles, canisters, drums, etc. Articles of plastic and components as described before may also comprise multilayered materials prepared par example according to the co-extrusion technique, wherein at least one layer is present comprising the ethylene homo- or copolymer of the instant invention.

The fluorination is performed preferably by elementary fluorine, however, mixed with an inert gas such as nitrogen or any noble gas, whereby also oxygen may be present in minor amounts up to 20 Vol.-%. Fluorine is thereby present in an amount of 0.5 to 10 Vol.-%, calculated on total volume of the gas mix. Preferably the inner surface of the plastic article is subjected to the fluorination after the thermoforming process either by blow molding or injection molding by introducing the gas mixture under a pressure of 1 to 20 bars at a gas temperature of from -20 to -190 ⁰ C, preferably from -20 to -100 °C, and maintaining the gas inside the blow molded article over a time period of from 10 s up to 10 min, preferably from 20 s to 8 min. The temperature of the inner surface of the hollow body made of the ethylene homo- or copolymer is thereby higher than the temperature of the fluorinating gas, as the reaction enthalpy is removed mainly by the fluorinating gas mix.

An especially advantageous embodiment of the invention is an integrated fluorination into the blow molding process, whereby especially the cold temperature of the fluorinating gas provides an additional cooling effect at the inner surface of the hollow article helping thereby to shorten the whole manufacturing process.

WORKING EXAMPLES

(I) Measurement Methods:

I. V. expressed as [dl/g] = Intrinsic viscosity according to ISO1628 (at 130 ⁰ C, 0,001 g/ml Decalin);

Density expressed as [g/cm ³ ] ISO 1183

HLMFR expressed as [g/10 min] (High Load Melt Flow Rate, measured at 190 ⁰ C and under a load of 21.6 kg) according to ISO 1133 Barrier properties according to mass loss of bottles (500 ml) filled with a mix of isooctane and toluene (1 to 1) comprising in addition 5 Vol.-% methanol after a certain time period.

Chimassorb ^® 944 was purchased from Ciba Inc. and Tinuvin ^® 770 DF from Ciba Inc. as well.

Irganox ^® 1010 and Irgafos ^® 168 were purchased from Ciba Inc.

(II) Experimental part:

High molecular mass polyethylene produced in a gas phase process in the presence of a chromium based Phillips catalyst having a HLMFR (190 °C/21 ,6 kg) of 6 g/10 min and a density of 0,946 g/cm ³ was treated with stabilizers as indicated in table 2. All polymers, except that of example 1 (comparison), were additionally stabilized with 400 ppm Irganox 1010 and 1100 ppm Irgafos 168. The powder was pelletized and stabilized in a ZSK53 extruder (Krupp Werner & Pfleiderer/Coperion, 1970) equipped with a dosing system for additivation.

Machine parameters Table 1 : W&P ZSK53

Polymer Stabilization Table 2:

Table 1 : Properties of pelletized samples; * ⁾ = not stabilized = comparison

From the pellets prepared in accordance with working examples 1 through 4 bottles having a planar bottom have been prepared by blow molding in a blow molding tool. The bottles had a volume of 500 ml. The bottles have been prepared at an inner pressure of 10 bars at a melt temperature of 195 ⁰ C and had a wall thickness of 1 mm, each. At a wall temperature within the range of from 90 to 100 ⁰ C the pressure was lowered to 2 bars and the fluorinating gas was introduced under a pressure of 10 bars.

As fluorinating gas a mix of 1 Vol.-% F ₂ , 2.6 Vol-% O ₂ and 96.4 Vol.-% N ₂ was employed having a temperature of -100 ⁰ C. After a contact time of 60 sec the fluorinating gas was removed by nitrogen. All bottles have been filled with 450 ml of a commercial super fuel having a methanol content of 3 Vol-.%. The bottles were closed gass tight and their exact weight was noted. Thereafter they were stored over a time period of 10 days, 20 days, 40 days and 60 days at a temperature of 50 ⁰ C in a heating chamber. After each time period their exact weight has been taken again and was compared with the noted weight of each bottle. The result is illustrated I the following table 3. Mass loss [g] after different time period of storage, Table 3:

Considering the results of the permeation tests as described above, it becomes clearly apparent that the presence of sterically hindered amine compounds in the ethylene polymer improves the barrier properties in combination with the fluorinating treatment significantly.