EP1309661A2 - Melange biodegradable de polymeres - Google Patents

Melange biodegradable de polymeres

Info

Publication number
EP1309661A2
EP1309661A2 EP01954255A EP01954255A EP1309661A2 EP 1309661 A2 EP1309661 A2 EP 1309661A2 EP 01954255 A EP01954255 A EP 01954255A EP 01954255 A EP01954255 A EP 01954255A EP 1309661 A2 EP1309661 A2 EP 1309661A2
Authority
EP
European Patent Office
Prior art keywords
polymer blend
acid
aliphatic
aromatic
particular according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01954255A
Other languages
German (de)
English (en)
Inventor
Harald Schmidt
Wolfgang Friedek
Petra Vogt
Jürgen LOERCKS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BioTec Biologische Naturverpackungen GmbH and Co KG
Original Assignee
BioTec Biologische Naturverpackungen GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BioTec Biologische Naturverpackungen GmbH and Co KG filed Critical BioTec Biologische Naturverpackungen GmbH and Co KG
Publication of EP1309661A2 publication Critical patent/EP1309661A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Definitions

  • the present invention relates to a biodegradable polymer blend, preferably based on renewable raw materials according to the preamble of claim 1, a method for producing a biodegradable polymer blend and uses of the polymer blend according to the invention.
  • Biodegradable polymers particularly those based on renewable raw materials, are increasingly finding their way into domains to which synthetic polymers or so-called plastics are reserved. This is not least due to the fact that the properties of these polymers are constantly being improved.
  • polymer materials are described, inter alia, on the basis of starch, the starch being brought into a largely crystalline form by the aid of low-molecular plasticizers, plasticizers, such as glycerol and sorbitol and other additives, so that it can be processed perfectly in a thermoplastic manner.
  • plasticizers such as glycerol and sorbitol and other additives
  • a number of other polymers are described as mixing partners in order to obtain improved properties.
  • the additional polymers such as chemically modified cellulose, aliphatic polyesters, polymer amides, etc., have at least some of them biodegradability and are partly based on renewable raw materials.
  • a major disadvantage of all of these proposed polymer mixtures lies in the fact that they contain plasticizers, plasticizers and other low molecular weight additives which can migrate out of the films, moldings etc. produced therefrom and are therefore unsuitable for a number of applications are, especially for use related to food contact.
  • the problem is to create a polymer mixture that is biodegradable, for example, according to DIN 54900 and, if possible, based on renewable raw materials and that can be used in contact with food, i.e. corresponds to the regulations of the EU directives 82/711 EEC and 90/128 EEC.
  • the object is achieved by means of a polymer blend according to the wording according to claim 1.
  • the polymer blend according to the invention obtainable by extrusion, contains at least one copolyester with aliphatic and aromatic blocks or a so-called th partially aromatic copolyester and at least 10% of an aliphatic polyester based on one or more hydroxycarboxylic acids and / or based on lactones with a glass transition point (TG) of at least 50 ° C.
  • TG glass transition point
  • the polymer blend according to the invention contains no low molecular weight plasticizers or plasticizers or other low molecular weight compounds which can migrate out of films or molded articles produced from the polymer blend.
  • EP 0 909 789 proposes polymer mixtures made from aliphatic and aliphatic / aromatic polyesters, but not obtainable by extrusion but by reaction of a mixture of the aforementioned components.
  • DE 198 48 505 proposes partially aromatic polyesters, some of which are made up of aliphatic hydroxycarboxylic acids, such as lactic acid. Again, the resulting polymers or polymer mixtures are not blends obtainable by extrusion.
  • DE 44 40 837 where polyether esters are mixed with high molecular weight hydroxycarboxylic acids such as polycaprolactone in a reaction vessel.
  • DE 23 31 826 discloses thermoplastic compositions containing copolyesters with aliphatic and aromatic block units and linear aliphatic polyester resins, which, however, are not biodegradable.
  • the thermoplastic compositions according to DE 23 31 826 have special electromechanical properties and in some cases include flame-retardant additives, which properties are biodegradable usually exclude.
  • the polymer mixtures proposed according to the invention are obtainable by extrusion or by compounding, and not essentially by chemical reaction of the polymer components with one another.
  • polyesters based on hydroxycarboxylic acids are polylactides, ie polymers based on lactic acid or derivatives of lactic acid.
  • Linear polylactides are mostly used, but branched lactic acid polymers can be used, with polyfunctional acids or alcohols, for example, being used as branching agents.
  • polylactides can be used which essentially consist of lactic acid or its Ci to C alkyl esters or mixtures thereof and, if appropriate, at least one aliphatic C to C 10 -
  • Dicarboxylic acid and at least one C 3 - to -C 0 alkanol with three to five hydroxyl groups are available.
  • those based on lactones can also be used as the aliphatic polyester, such as polycaprolactone or polymers based on hydroxybutyric acid, hydroxyvaleric acid and / or derivatives or mixtures thereof.
  • Polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyesters are particularly suitable.
  • polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolyester (PHBV) By adding polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolyester (PHBV), an increased water vapor barrier property can be achieved in the polymer blend according to the invention.
  • the reduced addition of polylactide or the omission of polylactides also results in an increased temperature resistance of moldings or foils produced from the partially aromatic polyester and PHBV to 100 ° C. or more.
  • the polymer blend contains at least one partially aromatic copolyester based on aliphatic and aromatic blocks as a mixing component to the aliphatic polyester based on hydroxycarboxylic acids and / or lactones mentioned.
  • the copolyester used according to the invention is produced, in addition to polyols, from aromatic or aliphatic dicarboxylic acids.
  • the essential components of the biodegradable copolyester contain acid components from at least one aliphatic and / or a cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof and / or at least one aromatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof.
  • the copolyester can contain at least one C 2 -C 12 -alkanediol and / or at least one C 5 - to C ⁇ -cycloalkanediol or mixtures thereof or optionally one or more components such as hydroxy compounds containing ether functions.
  • the copolyester can be obtained by polycondensation of at least one diol, for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol, on the other hand, with at least one aromatic dicarboxylic acid, such as terephthalic acid and optionally at least tens of an aliphatic dicarboxylic acid, such as adipic acid and / or sebacic acid.
  • at least one diol for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol, on the other hand, with at least one aromatic dicarboxylic acid, such as terephthalic acid and optionally at least tens of an aliphatic dicarboxylic acid, such as adipic acid and / or sebac
  • the carboxylic acids with a larger number of carbon atoms can be used for the production of the copolyester according to the invention, for example with up to 30 carbon atoms.
  • the ester-forming derivatives of the aliphatic or cycloaliphatic dicarboxylic acids mentioned, which can also be used, are, in particular, the di-C 1 to C 6 -alkyl esters, such as diethyl, diethyl, di-n-propyl, di-isopropyl, To name di-n-butyl ester, etc.
  • Anhydrides of the dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as mixtures of two or more thereof.
  • Aromatic dicarboxylic acids to be preferably used are generally those having 8 to 12 carbon atoms and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2, 6-naphthoic acid and 1, 5-naphthoic acid, as well as ester-forming derivatives thereof. Anhydrides of dicarboxylic acids are also suitable ester-forming derivatives. However, aromatic dicarboxylic acids with a larger number of carbon atoms, for example up to 20 carbon atoms, can also be used.
  • the aromatic dicarboxylic acids like also the aliphatic and / or cycloaliphatic dicarboxylic acids and / or their ester-forming derivatives, can be used individually or as mixtures of two or more thereof.
  • Preferred diols are branched or linear alkanediols having 2 to 12 carbon atoms, preferably having 4 to 6 carbon atoms or cycloalkanediols having 5 to 10 carbon atoms.
  • alkanediols examples include ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 2, 2-dimethyl-l, 3-propanediol, cyclopentanediol, 1, -cyclohexanediolmethanol, etc., to name but a few call.
  • other components can be used to produce the copolyester according to the invention, such as, for example, dihydroxy compounds, such as, for example, diethylene glycol or polyethylene glycol.
  • copolyesters mentioned above are only examples and can be supplemented by further possible partially aromatic copolyesters, reference being made in this connection to DE 198 49 448, in which such copolyesters described for the production of the polymer blend according to the invention are described are.
  • At least the partially aromatic copolyester composed of aliphatic and aromatic polyester together with the aliphatic polyester based on hydroxycarboxylic acids and / or lactones must now be mixed in an extruder, for example in a co-rotating extruder operating in the same direction, in a temperature range of approx. 120-220 ° C.
  • the temperature control depends on the starting materials used and in particular the specific melting points of the materials used. Degassing, which is common in extruders, takes place along the extruder, so that in particular during extrusion the water content in any case ⁇ 1% by weight. % is, so that foaming or the formation of bubbles in the extrudate can be avoided.
  • the extrudate is cooled and usually passed through a water bath and conditioned.
  • Films can now be produced from the polymer blends proposed according to the invention, such as packaging films in the food sector.
  • a polylactide of at least 20% transparent films can be produced.
  • partially aromatic copolyesters increased flexibility is achieved in the film, similar to films made from low-density polyethylene (LDPE). If, on the other hand, a low proportion of aromatic polyesters is used in the order of approximately 50%, the result is rather stiff films, similar to those made from high-density polyethylene (HDPE).
  • HDPE high-density polyethylene
  • the polymer blend proposed according to the invention can be used not only for foils, but also for applications in the injection molding field, for coatings, etc.
  • the great advantage of the polymer blends according to the invention is that they are so-called plasticizer-free compounds, which are particularly useful for contact are suitable with food, ie so for food packaging.
  • biodegradable e.g. according to DIN standard V 54900, i.e. they are compostable.
  • suitable additives such as 20%, preferably approx. 25 - 30% of native starch can be given antistatic properties.
  • the polymer blends according to the invention produced in this way are particularly suitable for applications in the electronic or electrical field where the material used in each case has to be antistatically equipped.
  • the native starch used had been predried during the production of the polymer blend according to the invention and has a residual moisture content of less than about 4 to 8% water.
  • Destructuring of the pre-dried starch is also ruled out under optimized conditions, such as longer residence times, screw geometry, which means that it is present in the polymer blend in a largely crystalline form, as required.
  • At least 10 By using at least 10, preferably at least 20% of a polylactide, they can be made opaque to crystal clear. However, they can also be colored in any way. Films can be produced with a paper-like handle and / or paper-like creasing properties, but nevertheless these films are fat-resistant, can be embossed and / or printed, which is particularly advantageous when used in the food sector. Finally, molded articles or molded parts can be produced by deep drawing.
  • Areas of application for the polymer blend according to the invention are in particular as flexible packaging in the food and non-food sector. It is primarily intended for use in so-called fast food packaging, which on the one hand has good fat resistance, but on the other hand should be compostable. It is of course additionally advantageous that the fast food packaging material produced according to the invention is produced entirely or partially on the basis of renewable raw materials.
  • thermoformable film for coating food packaging such as starch or cellulose-foamed packaging (egg carton),
  • An essential aspect of the polymer blends according to the invention lies in the migration values which correspond to the requirements of the EU guidelines.
  • plasticizer-free compounds are possible in order to be able to provide suitable materials, in particular in the food or fast food sector.
  • Global migration values of blends for example based on thermoplastic or destructurized starch, are substantially higher than the values now achieved with the polymer blends according to the invention due to the migration of the plasticizers contained, and thus mostly above the limit for use in contact with food.
  • water vapor permeability is lower than has previously been possible with the starch blends known from the prior art.
  • the water vapor permeability can be decisively reduced, in particular by the increased proportion of polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolymer.
  • Migration test at 70 ° C, 30 min. meets the requirements for fast food (migration limit according to EU guidelines is 10 mg / dm 2 or 60 milligrams per kilogram of food)
  • Polyhydroxybutyric acid / valeric acid copolyester 20% Water vapor permeability (WVTR) ⁇ 4 g / m 2 and day - measured at 23 ° C and 60% relative humidity, and
  • Temperature resistance 70 - 80 ° C can be increased to over 100 ° C without adding E-copla.
  • Starch is native starch, such as potato or corn starch.
  • Polyester 1 terephthalic acid-butanediol-adipic acid copolyester (Ecoflex)
  • Polyester 2 poly (butylene) succinate or poly (butylene) - succinate / adipate (Biomax 6929 from DuPont)
  • Fillers e.g. Talc or kaolin
  • B polyol ester
  • C natural wax
  • E-copla 6200 D from Cargill Dow Polymers Lacea H 100 J, Lacea H 100 E, Lacea H 100 PL (both from Mitsui Chemicals) and Ecopla 3000 D from Cargill were used as polylactide Dow Polymers.
  • Example 11 shows a clear difference in the water vapor permeability, in Example 11, in which 19.9% of a mixture of polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyester shows a significantly lower water vapor permeability.
  • PLA polylactide (EcoPla 6200 D) and 44.6% polyester 1 (Ecoflex sbx) with 0.4 slipping agent (loxamide / manufacturer Cognis-Erucaklaklamid) were in a twin-screw extruder (Wemer & Pfleiderer ZSK.40) to a thermoplastic melt with a Final melting temperature of 185 ° C compounded and granulated.
  • the polymer mixture thus obtained had an MFI - (g / 10 min) 190 ° C., 5 kg - of 9.5.
  • a transparent film as a tube with a width of 275 mm and a wall thickness of 0.08 mm was produced from this polymer blend granulate on a Collin film blowing system.
  • the film is easily printable and weldable at approx. 110 ° C. From this tube a beverage packaging in the dimensions 275 mm x 140 mm x 0.08 was produced by welding. This tubular bag packaging was infested with milk as a sensitive drink and filling material, stored in the refrigerator at 8 ° C and on storage properties both in terms of content and also tested on the packaging material.
  • tubular bag packaging survived all drop tests from a height of 1 m undamaged.
  • the tube bag packaging remained unchanged in its optical and physical properties after a storage time of 72 hours.
  • Tubular film packaging made of polymer blend Example 29, film wall thickness 0.08 mm
  • beverage packaging in the form of foil bags, produced according to Example 29, was tested with orange juice. This confirmed the good protective function for beverages of the polymer blend according to the invention as packaging means and the suitability of the material for use as beverage packaging, as a coating for beverage packaging and / or as an liner for liquid or pasty food packaging. - 21 -
  • Example 29 it was possible to demonstrate impressively that the polymer blends proposed according to the invention are suitable for food packaging and in particular for packaging beverages.
  • Either the tubular film packaging proposed in Example 29 can be produced from the polymer blends according to the invention, or else beverage packaging which has a cardboard reinforcement on the outside as mechanical protection and a film sleeve on the inside consisting of the polymer blend according to the invention.
  • any containers using a polymer blend according to the invention for holding liquid fillings or viscous or pasty fillings, in particular for holding the above-mentioned beverage or other liquid foodstuffs, such as, for example, cooking oil.
  • the so-called "slipping agent Loxiol EP 728" is a polyol partial ester from Henkel KgaA,
  • Loxiol EP 728 is particularly suitable for improving the flow properties in injection molding - 22 -
  • the composition was obtained by compounding in a twin-screw extruder (Werner & Pfleiderer, ZSK 40) to give a homogeneous melt at 170 ° C. melt temperature and complete degassing.
  • the granules obtained have an MFI ((g / 10 min.) 190 ° C., 5 kg) of 13.7 and a residual moisture of 0.2%.
  • the granulate is suitable for further processing as blown film, flat film and injection molding.
  • the almost transparent films are plasticizer-free, easy to print and low-sweat.
  • a polymer blend contains at least part of aromatic polyester based on aliphatic and aromatic blocks and at least one aliphatic polyester produced based on, among others, hydroxycarboxylic acids and / or lactones and / or their derivatives. Depending on the proportion of different materials, different ones can be - 23 -
  • the polymer blend is at least almost free of plasticizer or free of low molecular weight components which can migrate out of films or moldings produced from the polymer blend according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne un mélange biodégradable de polymères obtenu par extrusion et contenant au moins un polyester partiellement aromatique et des blocs aliphatiques et aromatiques. Au moins 10 % en poids de ce mélange avec le polyester partiellement aromatique, contient un polyester aliphatique sur la base d'au moins un acide hydroxycarboxylique et/ou d'au moins une lactone, ce polyester aliphatique possédant un point de transition vitreuse (TG) supérieur à 50°. Ce mélange de polymères ne contient avantageusement aucun plastifiant et, de plus, est constitué par des matériaux pouvant être régénérés.
EP01954255A 2000-08-11 2001-08-07 Melange biodegradable de polymeres Withdrawn EP1309661A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH156800 2000-08-11
CH15682000 2000-08-11
CH17472000 2000-09-07
CH174700 2000-09-07
PCT/IB2001/001407 WO2002014430A2 (fr) 2000-08-11 2001-08-07 Melange biodegradable de polymeres

Publications (1)

Publication Number Publication Date
EP1309661A2 true EP1309661A2 (fr) 2003-05-14

Family

ID=25738986

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01954255A Withdrawn EP1309661A2 (fr) 2000-08-11 2001-08-07 Melange biodegradable de polymeres

Country Status (7)

Country Link
US (1) US20030187149A1 (fr)
EP (1) EP1309661A2 (fr)
JP (1) JP2004506773A (fr)
CN (1) CN1446247A (fr)
AU (1) AU2001276597A1 (fr)
CA (1) CA2419146A1 (fr)
WO (1) WO2002014430A2 (fr)

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JP2004506773A (ja) 2004-03-04
WO2002014430A2 (fr) 2002-02-21
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CA2419146A1 (fr) 2003-02-06
WO2002014430A3 (fr) 2002-08-15
CN1446247A (zh) 2003-10-01

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