Patent Application
20090270564
The present invention concerns the field of packaging, more particularly in relation with the packaging of food and beverages.
The present invention is related to a method for the direct conversion of a polyester melt as it is after a melt polycondensation process to articles for packaging purposes, in particular for the production of hollow bodies, thermoformed sheets and films, said articles containing an amount of acetaldehyde less than 10 ppm.
The invention is also directed to the packaging articles obtained by this process.
The production of polyester for the purpose of the manufacture of shaped polyethylene terephthalate food packaging products like hollow bodies, thermoforming sheets and films is described in details for instance in U.S. Pat. No. 4,340,721. The summary of the main teaching of this patent is the melt phase polycondensation of polyester in presence of co-monomers like isopthalic acid, naphthalenedicarboxylic, adipic and/or sebacinic acid, and/or ester-forming derivatives thereof, which is followed by the conversion of the precursor melt to a granulate. This granulate, which is containing higher amounts of acetaldehyde (hereafter referred to as AA) and presents an intrinsic viscosity (hereafter referred to as IV) between 0.55 and 0.70 dl/g is treated in the solid phase polycondensation according to published French Patent FR-A-2 425 455 to increase the intrinsic viscosity to a range between 0.65 and 1.0 dl/g and to reduce the content of acetaldehyde to less than 1.25 ppm.
To overcome the disadvantage of this multistep method containing a melt phase polycondensation, solid phase polycondensation, pre-drying and shaping of packaging products a number of methods have already been suggested to reduce process complexity, energy consumption, material losses and investment cost.
U.S. Pat. No. 5,656,221 describes a method for direct production of shaped packaging material made of thermoplastic polyesters where an inert gas is introduced into the polyester melt and distributed uniformly in the melt immediately after its discharge from the polycondensation reactor. In this method, 0.05 to 1.0 weight % of an amide compound with a low volatility like MXD6 nylon is added to the polyester melt directly next to the gas inlet. Finally, the polyester melt is subjected to a vacuum degassing immediately before the shaping.
U.S. Pat. No. 5,656,719 describes a method for producing bottle preforms from the melt of polyethylene terephthalate and/or its copolyesters, which includes selectively introducing an inert gas into the continuous flow or partial flow of the polyester melt from a poly-condensation having an intrinsic viscosity between 0.5 and 0.75 dl/g, subsequently bringing the melt to an acetaldehyde content below 10 ppm in a melt after-condensation reactor and to an intrinsic viscosity of 0.75 to 0.95 dl/g and thereafter guiding the melt into an injection moulding tool and processing the same.
WO 97/31968 describes a method comprising the steps of a) melt reacting at least one glycol and at least one dicarboxylic acid to form a polyester having an IV of at least about 0.50 dl/g, wherein said at least one glycol is selected from the group consisting of glycols having up to 10 carbon atoms and mixtures thereof and said dicarboxylic is selected from the group consisting of alkyl dicarboxylic acids having 2 to 16 carbon atoms, aryl dicarboxylic acids having 8 to 16 carbon atoms and mixtures thereof, b) forming said polyester into shaped articles directly from step a) and comprising the step of vacuum devolatilizing prior direct melt to mould method for forming polyester articles.
US Patent Application No. 20050161863 describes a method of making shaped articles from a highly condensed polyester melt and especially preforms for the blow moulding of food and especially beverage containers where a melt is continuously withdrawn from the polycondensation reactor and is fed to the shape-imparting units, especially a multiplicity of injection-moulding machines without solidification between the final reactor and the injection moulders and without degassing between the final reactor and the injection moulding machines. To reduce the acetaldehyde content of the polyester melt, the adding of a phosphorus-containing substance or an acetaldehyde-reducing substance or mixture of substances in solid form or as a slurry before said melt enters the moulding unit, is suggested.
The teachings of these inventions comprise the removal of acetaldehyde by injecting inert gas to the polyester melt after the polycondensation reactor, purging and subsequent devolatization of the melt applying a vacuum degassing unit, the addition of acetaldehyde scavenging substances or the combination of both methods. Especially during the last decade it has been discovered that low molecular weight acetaldehyde scavengers have the potential to migrate from the container wall, whereas high molecular weight acetaldehyde scavengers like MXD6-nylon or its oligomers are less active with the result of high application concentration. In any case the use of acetaldehyde scavengers induces additional cost.
It is known that acetaldehyde exists in the polyester melt in two configurations which are firstly solved as free acetaldehyde and secondly chemically bound as vinyl-ester end-groups. It is also known that the vinylester end-groups are preferentially created by dehydration of free OH-end-groups.
To reduce the number of free OH-end-groups and with this, the rebuilding rate of acetaldehyde during the extrusion and injection moulding of state of the art bottle PET produced by melt polycondensation and SSP, U.S. Pat. No. 4,361,681 is suggesting to add phthalic anhydride or succinic anhydride at any time after the melt polycondensation and prior injection moulding. Disadvantage of this process is that the reactive anhydride has to be dosed exactly and the reaction temperature and time must be accurately adjusted to guarantee a 100% conversion of anhydride with the OH-end-groups to avoid that non-reacted anhydride is present in the wall of the beverage container.
Another method to reduce the content of acetaldehyde during melt polycondensation which is described in US patent application 20050049391 is suggesting the addition of special catalyst substances like active vinyl ester transesterification catalysts for catalyzing conversion of the vinyl ester end groups to acetaldehyde, heating the polyester, and providing egress for the acetaldehyde from the polyester. These transesterification catalysts can be selected from the group consisting of Group Ia and Group IIa metals. Disadvantage of this method is that the real source of vinyl ester end groups which are the OH-end-groups is not reduced.
Gas purging and devolatization as well as acetaldehyde scavengers are only removing or absorbing the free acetaldehyde. Disadvantage of the acetaldehyde scavengers are high additive cost and potential migration from the packaging wall. The addition of dianhydrides is reducing the OH-end-groups but does not guarantee that no non-reacted dianhydrides are present in the wall of the final beverage.
The addition of transesterification catalyst which is converting the vinylester end-groups is reducing the source of subsequent acetaldehyde rebuilding but will not reduce the number of OH-end-groups.
Therefore, there is still a need for a method for the direct manufacturing of polyester for packaging from polyester melt derived from polycondensation reactor, in which the packaging polymer can be provided with the desired low content of acetaldehyde without the disadvantages of the described production methods.
The problem of the present invention is solved by a method as described in claim 1.
Special embodiments and advantages are set forth in the depending claims.
The present invention also provides packaging articles with a low acetaldehyde content as claimed in claim 10.
According to the present invention, a method for the direct production of polyester articles for packaging purposes, in particular for hollow bodies, thermoformed sheets and films, said articles containing an amount of acetaldehyde less than 10 ppm is proposed.
The method according to the present invention is essentially comprising the following steps:
a) providing a polyethylene terephthalate based polymer melt which is directly produced by conversion of more than 90 weight % of terephthalic acid or dimethyl terephthalate and ethylene glycol, said polymer melt having an intrinsic viscosity (IV0) at the outlet of the polycondensation reactor in a range of 0.5 dl/g to 0.90 dl/g, preferably between 0.6 and 0.7 dl/g,
b) adding to said polymer melt, a mixture of at least one inert and at least one reactive substances which reacts with the —COOH and/or —OH and/or —COO—CH═CH2 end groups of the polyester and/or with the ester bonds of the polyester chain in order to at least cause partial hydrolysis and/or acidolysis and/or alcoholysis and/or ammonolysis and/or hydrazinolysis and/or addition reaction to said end groups combined with acidolysis and/or a combination of these reactions thereby causing an increase of the sum of end groups from an initial level SE0 at the end of step a) to a first level SE1 at the end of this step,
c) removing the low molecular weight monomer substances having a molecular weight ≦500 g/mol present and formed, the non-reacted reactive substance(s) and the inert substance(s) added during previous step b) after a reaction time of >1 second and <3600 seconds by submitting the polymer melt to a degassing step consisting in essentially applying a vacuum of 0.05-800 mbar causing a partial polycondensation, which thereby causes a decrease of the sum of end groups from said first level SE1 to a second sum of end group level SE2 at the end of this step and,
d) converting directly the previously obtained polymer melt into the desired articles.
The polyester melt of the process according to the present invention is containing up to 10 weight % of one or a mixture of co-monomers selected from the group consisting in:
diethylene glycol, triethylene glycol, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, cyclohexane dimethanol, pyromellitic acid, trimellitic acid, pentaerythrol, neopentylglycol, triethylene glycol tetraethylene glycol, pentaethylene glycol, polyethylenglycol and polypropylenglycol.
According to a first feature of the present invention, the amount of acetaldehyde or AA contained in the polymer melt at the outlet of the polycondensation reactor is comprised between 1 and 150 ppm.
The added amount of reactive substance(s) during step b) is sufficient to reach a first level of the sum of end groups SE1 after this treatment, which is increased by ≧1% and ≦30%, preferably increased by ≧4% and ≦8% compared to the sum of end group level SE0 of the polymer melt at the end of step a).
Purpose of the addition of said reactive substances is to provide for an internal washing method which is removing vinyl ester end groups and reducing the number of end groups which are source of vinyl ester end groups.
According to the invention, the adding of a reactive substance or substance mixture to the polymer melt after the polycondensation reactor during step b) is carried out continuously.
Advantageously, the said reactive substance or substance mixture added during step b) is able to react with end groups and/or to terminate ester bondings of the polyester chain within a reaction time of >1 second and <3600 seconds.
According to another feature, said added reactive substance or substance mixture is applied during step b) with an inert gaseous carrier, preferably selected in the group consisting of: nitrogen, hydrogen, helium, argon, carbon dioxide, ethane, propane, butane, n-hexane, cyclohexane or mixtures out of these substances.
According to the invention, the reactive substance or substance mixture added during step b) is selected in the group consisting of:
and wherein the condition of aggregation of the above described reactive substance or substance mixture is liquid and/or gaseous and/or supercritical.
The reactive substance or substance mixture added during step b) is able to increase the total number of end groups and/or destruct the polymer chain partially and/or react with OH-end-groups under endcapping and/or replace vinyl-ester end groups.
According to another feature of the present invention, the degassing step carried out in step c) is carried out in an environment of 0.05 mbar to 800 mbar, preferably between 0.1 and 10 mbar to remove said added inert substance(s), a possible excess amount of reactive substance(s), the decomposition products caused by said reactive substance(s) and the common split and side products, which may occur during polyester production and wherein the sum of end group SE2 of the polymer melt after said degassing step is inferior or equal to the end group level SE1 existing at the beginning of said degassing step.
In the case where the vacuum degassing does not achieve molecular weight increase SE2 can be equal to SE1.
As an example, the polymer melt is entered a device like for instance a twin or multi screw extruder or a spiral reactor where the melt is distributed and exposed to a degassing zone containing vacuum environment to remove the non-reactive inert substances, the excess amount of reactive substances, the quoted decomposition products caused by said reactive substances and the common split and side products as referred to above.
Preferably, the levels of sum of end groups in the polymer melt satisfies:
SE0<SE1 and SE0<SE2 and SE2<1,3SE0
wherein
SE0=level of the sum of end groups at the end of step a),
SE1=level of the sum of end groups at the end of step b),
SE2=level of the sum of end groups at the end of step c).
Advantageously, the said step b) is carried out by operating at least one dosing system for common additives like colour, stabilizers, acetaldehyde scavengers, oxygen scavengers, UV absorbers, optical brighteners, antistatic agents and/or surface modificator.
Those systems are well known by the person skilled in the art and do not need to be detailed any further here. After departing the degassing unit, the polyester melt is immediately converted to the desired article for packaging purposes like preforms, bottles or cast films.
The present invention also encompasses polyester articles for packaging purposes with an acetaldehyde content less than 10 ppm, in particular hollow bodies, especially bottles, thermoformed sheets and films, especially cast films, characterised by the fact that they are obtained by a method according to the present invention.
According to the invention the said degassing unit can comprise commonly used dosing systems which feed usually applied additives for colour, stabilizers, acetaldehyde scavengers, oxygen scavengers, UV absorbers, optical brighteners, antistatic agents, surface modification to the polyester melt. Those systems are well known by the person skilled in the art and do not need further description here. After departing the degassing unit the polyester melt is immediately converted to preforms, bottles and cast films.
The present invention will be better understood thanks to the following description and drawing of a preferred embodiment of said invention given as a non limitative example thereof.
The unique figure is a schematical functional representation of the method according to the present invention.
As shown on said figure, a state of the art polycondensation plant or reactor 1 of a daily capacity of 220 t of bottle grade polyester melt was chosen, in which may be carried out the operations of paste preparation, esterification(s), prepolycondensation and in which terephthalic acid, mono ethylene glycol and isopthalic acid may be converted to a base resin with the following specification (at the outlet of the melt finisher or reactor 1):
The intrinsic viscosity IV is measured under the following conditions: 0.5 g of polyester are dissolved in 0.11 of a solvent consisting of phenol and 1,2-dichlorobenzene (3:2 weight parts), the relative viscosity of this solution is analyzed at 25° C. applying the method of Ubbelohde. The intrinsic viscosity is calculated from the relative viscosity by extrapolation to 0%.
Carboxyl end groups (—COOH) are analyzed by the following method:
The polyester is dissolved during heating in a solvent consisting of 70 weight % o-cresol and of chloroform (70:30 weight parts), and the content of —COOH groups is photometrically determined with 0.05 n of ethanolic potassium hydroxide against bromothymol blue.
Acetaldehyde is analyzed as following:
Analysis of residual of AA in PET packaging (resins, preforms and bottles) is performed by GC-Flame Ionising Detector on the headspace generated by heating grinded material at high temperature into a sealed vial.
Measurement is done according to the AFNOR method XP T90-210 standard defined by the French Ministry of Health, document ref. DGS/PGE/1.D.-no1526 (December 1999).
As shown in
In table 1 the results of the examples 1 to 7 and the comparative examples V1-V2 are described for a polyester article for packaging purposes which consists in a conventional preform.
All examples of table 1 have the same SE0=26 mequ/kg.
As can clearly been seen from table 1, the preforms of the invention contain up to 5 times less AA as the preforms of comparative examples V1 and V2.
The present invention is, of course, not limited to the preferred embodiment described and represented herein, changes can be made or equivalents used without departing from the scope of the invention defined by the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 06360009.2 | Mar 2006 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2007/052999 | 3/29/2007 | WO | 00 | 9/18/2008 |
