EP3032972A1 - Catalytically degradable plastic and use of same - Google Patents

Catalytically degradable plastic and use of same

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Publication number
EP3032972A1
EP3032972A1 EP14744596.9A EP14744596A EP3032972A1 EP 3032972 A1 EP3032972 A1 EP 3032972A1 EP 14744596 A EP14744596 A EP 14744596A EP 3032972 A1 EP3032972 A1 EP 3032972A1
Authority
EP
European Patent Office
Prior art keywords
degradable plastic
titanium dioxide
catalytically
catalytically degradable
transition
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Withdrawn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
EP14744596.9A
Other languages
German (de)
French (fr)
Inventor
Dirk HÖLTER
Wolfgang Koppe
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.)
Cerdia Produktions GmbH
Original Assignee
Solvay Acetow GmbH
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 Solvay Acetow GmbH filed Critical Solvay Acetow GmbH
Priority to EP14744596.9A priority Critical patent/EP3032972A1/en
Publication of EP3032972A1 publication Critical patent/EP3032972A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068—Biodegradable or disintegrable
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate

Definitions

  • the invention relates to a catalytically degradable plastic, in particular with a content of cellulose esters and the use thereof, in particular in filter tows for the production of filter plugs of filter cigarettes.
  • Plastics that may or may end up in the environment at the end of their lifecycle should be degradable within a short period of time under the conditions prevailing there in order to minimize exposure to pollution.
  • the duration of their decomposition depends strongly on the external conditions. So the degradation under composting conditions is faster than in likewise
  • Anatase modification which can decompose organic materials by photocatalytic action. Anatase absorbs light in the ultraviolet range of the
  • the present invention seeks to provide further under catalytically degradable plastics under environmental conditions.
  • this catalytically degradable plastic is to find advantageous application as a shaped body, in particular in a filter tow for producing a filter plug of a cigarette filter.
  • this object is achieved by a catalytically degradable plastic of the type described above in that the catalytically degradable plastic contains a catalytically active transition-metal-modified titanium dioxide, especially in finely divided form, e.g. dispersed in the plastic.
  • transition metal-modified means, in particular, that the titanium dioxide is oxidized by addition, (for example, mixing,
  • Impregnation, co-precipitation, co-crystallization of metals, metal compounds or metal complexes of the transition metals.
  • Transition metals are metals of Groups 3 to 12 of the Periodic Table (IUPAC, 2013), with the exception of titanium such as chromium, cobalt, copper, nickel, silver, gold, vanadium, zirconium, tungsten, molybdenum, tantalum, niobium, manganese, Zinc and iron. Preference is given to non or low toxic
  • Transition metals in particular manganese, zinc and iron. Iron is especially preferred.
  • Specific suitable iron-modified titanium oxides containing ferric oxide have been disclosed in WO-A-2012/139726, the contents of which are incorporated by reference into the present application.
  • the modification of the titanium dioxide with transition metals leads to an improvement in the catalytic activity for the degradation of plastics without the performance characteristics of the
  • plastic is a cellulose ester, cellulose acetate,
  • Degree of substitution is preferably between 1.5 and 3.0, in particular between 2.2 and 2.7, especially in the case of cellulose acetate. It is expedient if the cellulose ester, in particular cellulose acetate, with respect to an advantageous degree of polymerization with respect to the average degree of polymerization Solution of the task is optimized. The optimum average degree of polymerization is between 150 and 500, in particular between 180 and 280 in the cellulosic ester.
  • Cellulo starter compositions can be catalytically degraded at high speed in the environment.
  • a suitable measure is, like the
  • the core of the invention thus lies in the selection of a transition-metal-modified titanium dioxide, which is transition-metal-modified on its surface or else in the entire volume. Preference is given to a transition-metal-modified titanium dioxide whose surface is transition-metal-doped. By doping the band gap of the semiconductor titanium dioxide is reduced and it can be used in comparison to undoped titanium dioxide and longer wavelength light for exciting a valence band electron and thus to activate the photocatalytic properties.
  • the crystallite size of the transition metal-doped titanium dioxide is expediently optimized, the crystallite size preferably being between 5 and 150 nm, in particular between 7 and 25 nm. In individual cases, it may be advantageous or even necessary, a coarse
  • Transition metal modified titanium dioxide to grind to the optimum
  • transition metal modified titanium dioxide has a density (ISO 787, Part 10) of 3.0 to 5.0 g / cm 3 , in particular from 3.5 to 4.2 g / cm 3 .
  • An advantageous effect also for a degradation of the cellulose ester-containing plastic is an optimization of the specific surface of the transition metal-modified
  • Titanium dioxide It is preferable that the BET specific surface area of the transition metal-doped titanium dioxide is greater than 100 m2 / g, in particular greater than 250 m 2 / g.
  • the inclusion of a transition-metal-modified titanium dioxide in the catalytically degradable plastic according to the invention has a particularly advantageous effect if the
  • Transition-metal-modified titanium dioxide is characterized with a compared to pure titanium dioxide increased light absorption in the range of ⁇ > 400 nm.
  • transition-metal-modified titanium dioxide to 0.1 to 5% by weight, in particular 0.3 to 1.5% by weight.
  • the transition metal content of the transition metal-modified titanium dioxide is not significantly limited. Preferably contains
  • transition metal-modified titanium dioxide transition metal in an amount of 0.05 to 5% by weight, in particular from 0.3 to 3% by weight.
  • the catalytically degradable plastic is essentially not based solely on cellulose esters.
  • Conventional additives such as e.g. Plasticizers, be included, so in the case of
  • a non-transition-metal-modified titanium dioxide in particular anatase, may be included in fine dispersion, especially in the case of the cigarette industry.
  • the content of the catalytically degradable plastic of cellulose ester is at least 60% by weight, in particular at least 90% by weight ,
  • the good catalytic degradability of the plastic according to the invention in particular, when the catalytically degradable plastic is converted into a shaped body, especially in fibers, films, especially deep-drawn films, especially for use as packaging materials, injection molded articles, thick-walled moldings, granules, microbeads , Pearls and vessels. Therefore, the further processing of these fibers into filter tows, with which filter rods and filter caps of
  • Filter cigarettes are produced. Such filter plugs found in the environment are degraded significantly faster than those containing unmodified titanium dioxide.
  • the method for producing the catalytically degradable plastic according to the invention is not particularly limited.
  • One possibility is the
  • the plastic in particular cellulose ester
  • the plastic is preferably dissolved in the customary manner, for example in acetone.
  • the relevant other ingredients such as the particular Transition metal modified titanium dioxide added to then perform the usual spinning in a drying channel.
  • Another embodiment of the dry-spinning process envisages mixing the relevant further constituents-apart from the plastic, in particular cellulose ester-in particular the transition metal-modified titanium dioxide, with a suitable solvent, for example acetone, and then adding the plastic, in particular cellulose ester. This mixture is then used in a drying channel for the usual spinning process.
  • Iron-modified TiO 2 is used according to the method disclosed in Example 1 of WO 2010/017989 in the production of a cellulose acetate-based filter rod.
  • the filter rod of the present invention exhibits improved degradability under environmental conditions compared to a filter rod made with unmodified TiO 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Abstract

A catalytically degradable plastic is described, with content of cellulose esters and also optionally of additives. A particular characterizing feature of this catalytically degradable plastic is that it contains a dispersed, catalytically active transition-metal-modified titanium dioxide.

Description

Katalytisch abbaubarer Kunststoff sowie dessen Verwendung  Catalytically degradable plastic and its use
Die Erfindung betrifft einen katalytisch abbaubaren Kunststoff, insbesondere mit einem Gehalt an Celluloseestem sowie die Verwendung desselben, insbesondere in Filtertows zur Herstellung von Filterstöpseln von Filterzigaretten. Diese Anmeldung beansprucht die Priorität der EP Anmeldung Nr. 13180137.5, auf deren gesamten Inhalt hiermit Bezug genommen und der für alle Zwecke eingeschlossen wird. The invention relates to a catalytically degradable plastic, in particular with a content of cellulose esters and the use thereof, in particular in filter tows for the production of filter plugs of filter cigarettes. This application claims the benefit of EP Application No. 13180137.5, the entire contents of which are hereby incorporated by reference and included for all purposes.
Kunststoffe, die am Ende ihres Lebenszyklus in die Umwelt gelangen oder gelangen können, sollten unter den dort herrschenden Bedingungen innerhalb kurzer Zeiträume abbaubar sein, um eine Belastung möglichst gering zu halten. Allerdings hängt auch bei Kunststoffen, die prinzipiell biologisch abbaubar sind, die Zeitdauer ihrer Zersetzung stark von den äußeren Bedingungen ab. So ist der Abbau unter Kompostierbedingungen schneller als in ebenfalls  Plastics that may or may end up in the environment at the end of their lifecycle should be degradable within a short period of time under the conditions prevailing there in order to minimize exposure to pollution. However, even with plastics that are biodegradable in principle, the duration of their decomposition depends strongly on the external conditions. So the degradation under composting conditions is faster than in likewise
Mikroorganismen enthaltenden Böden. Deutlich langsamer ist der Bioabbau, wenn die Bedingungen für die dazu notwendigen Mikroorganismen Soil containing microorganisms. Biodegradation is significantly slower if the conditions for the necessary microorganisms
unzureichend sind. Dies ist der Fall, wenn der entsprechende Kunststoff ganz oder teilweise auf einer Oberfläche, zum Beispiel Steinplatten, Asphalt, Sand, Erde oder Gras, liegt. Unter diesen Umständen sind andere oder zusätzliche Abbaumechanismen notwendig. Besonders geeignet ist in diesen Fällen die photokatalytische Zersetzung unter Einwirkung von Licht. Diese kann der alleinige Mechanismus für einen vollständigen Abbau des Materials sein, aber auch eine unterstützende Wirkung für andere Abbaumechanismen haben. are insufficient. This is the case when the corresponding plastic is wholly or partially on a surface, for example stone slabs, asphalt, sand, earth or grass. Under these circumstances, other or additional degradation mechanisms are necessary. Particularly suitable in these cases is the photocatalytic decomposition under the action of light. This may be the sole mechanism for complete degradation of the material but may also have a supporting effect on other degradation mechanisms.
Seit langem ist bekannt, dass Titandioxid, insbesondere in der  It has long been known that titanium dioxide, especially in the
Anatasmodifikation, durch photokatalytische Wirkung organische Materialien zersetzen kann. Anatas absorbiert Licht im ultravioletten Bereich des Anatase modification, which can decompose organic materials by photocatalytic action. Anatase absorbs light in the ultraviolet range of the
Spektrums, wobei durch die nachfolgenden Elektronenübertragungen Radikale entstehen, die einen durch Kettenmechanismus bewirkten Abbau einleiten. Spectrum, resulting in the subsequent electron transfer radicals, which initiate a chain mechanism caused by degradation.
In Folge eines verstärkten öffentlichen Focus in den 1990er Jahren auf den Verbleib von Kunststoffmaterialien nach der Erfüllung ihres Einsatzzweckes wurden verstärkt Arbeiten zum Abbau von Celluloseestem und daraus hergestelltem Filtertow in der Umwelt durchgeführt.  As a result of increased public focus in the 1990s on the fate of plastic materials after fulfilling their intended use, work has increasingly been carried out on the degradation of cellulose esters and filter tows made therefrom in the environment.
Die Anmelderin hat bereits zufriedenstellende Lösungen für den photokatalytischen Abbau von polymeren Celluloseestem zur Verfügung gestellt (siehe z.B. WO-A-2010/017989) in der die Abbaubarkeit durch Applicant has already provided satisfactory solutions for the photocatalytic degradation of polymeric cellulose esters (see, for example, WO-A-2010/017989) in the degradability by
kohlenstoffmodifiziertes Titandioxid erhöht wird. carbon-modified titanium dioxide is increased.
Ausgehend von dem vorstehend geschilderten Stand der Technik lag der Erfindung die Aufgabe zugrunde, weitere unter Umweltbedingungen katalytisch abbaubare Kunststoffe anzugeben. Darüber hinaus strebt es die Erfindung an, dass dieser katalytisch abbaubare Kunststoff als Formkörper vorteilhafte Anwendung finden soll, insbesondere in einem Filtertow zur Herstellung eines Filterstöpsels eines Zigarettenfilters.  Based on the above-described prior art, the present invention seeks to provide further under catalytically degradable plastics under environmental conditions. In addition, it aims at the invention that this catalytically degradable plastic is to find advantageous application as a shaped body, in particular in a filter tow for producing a filter plug of a cigarette filter.
Erfindungsgemäß wird diese Aufgabe durch einen katalytisch abbaubaren Kunststoff der eingangs bezeichneten Art dadurch gelöst, dass der katalytisch abbaubare Kunststoff ein katalytisch wirksames, übergangsmetallmodifiziertes Titandioxid enthält, dies insbesondere in fein verteilter Form, z.B. in dem Kunststoff dispergiert.  According to the invention this object is achieved by a catalytically degradable plastic of the type described above in that the catalytically degradable plastic contains a catalytically active transition-metal-modified titanium dioxide, especially in finely divided form, e.g. dispersed in the plastic.
„Übergangsmetallmodifiziert" bedeutet im Sinne der vorliegenden Erfindung insbesondere, dass das Titandioxid durch Zusatz, (z.B. Mischen, For the purposes of the present invention, "transition metal-modified" means, in particular, that the titanium dioxide is oxidized by addition, (for example, mixing,
Imprägnieren, Ko-Fällen, Ko -Kristallisieren) von Metallen, Metallverbindungen oder Metallkomplexen der Übergangsmetalle verändert wurde. Impregnation, co-precipitation, co-crystallization) of metals, metal compounds or metal complexes of the transition metals.
„Übergangsmetalle" sind Metalle der Gruppen 3 bis 12 des Periodensystems (IUPAC, 2013), mit Ausnahme von Titan wie z.B. Chrom, Kobalt, Kupfer, Nickel, Silber, Gold, Vanadium, Zirkon, Wolfram, Molybdän, Tantal, Niob, Mangan, Zink und Eisen. Bevorzugt sind nicht oder wenig toxische "Transition metals" are metals of Groups 3 to 12 of the Periodic Table (IUPAC, 2013), with the exception of titanium such as chromium, cobalt, copper, nickel, silver, gold, vanadium, zirconium, tungsten, molybdenum, tantalum, niobium, manganese, Zinc and iron. Preference is given to non or low toxic
Übergangsmetalle, wie insbesondere Mangan, Zink und Eisen. Eisen ist ganz besonders bevorzugt. Spezielle geeignete eisenmodifizierte Titanoxide, die Eisen(III)oxid enthalten, wurden in der WO-A-2012/ 139726 offenbart, deren Inhalt durch Bezugnahme in die vorliegende Anmeldung aufgenommen wird. Transition metals, in particular manganese, zinc and iron. Iron is especially preferred. Specific suitable iron-modified titanium oxides containing ferric oxide have been disclosed in WO-A-2012/139726, the contents of which are incorporated by reference into the present application.
Überraschenderweise führt die Modifizierung des Titandioxids mit Übergangsmetallen zu einer Verbesserung der katalytischen Aktivität zum Abbau von Kunststoffen ohne die Gebrauchseigenschaften der  Surprisingly, the modification of the titanium dioxide with transition metals leads to an improvement in the catalytic activity for the degradation of plastics without the performance characteristics of the
Kunststoffprodukte wesentlich zu beeinträchtigen. Significantly affect plastic products.
Wenn der Kunststoff ein Celluloseester ist, sind Celluloseacetat,  If the plastic is a cellulose ester, cellulose acetate,
Cellulosepropionat, Cellulosebutyrat, Celluloseacetatpropionat und/oder Celluloseacetatbutyrat besonders bevorzugt. Der durchschnittliche  Cellulose propionate, cellulose butyrate, cellulose acetate propionate and / or cellulose acetate butyrate are particularly preferred. The average
Substitutionsgrad (DS) liegt vorzugsweise zwischen 1,5 und 3,0, insbesondere zwischen 2,2 bis 2,7, dies insbesondere beim Celluloseacetat. Zweckmäßig ist es, wenn der Celluloseester, insbesondere Celluloseacetat, bezüglich des durchschnittlichen Polymerisationsgrads im Hinblick auf eine vorteilhafte Lösung der gestellten Aufgabe optimiert ist. Der optimale durchschnittliche Polymerisationsgrad liegt bei dem Cellulo Seester zwischen 150 und 500, insbesondere zwischen 180 und 280. Degree of substitution (DS) is preferably between 1.5 and 3.0, in particular between 2.2 and 2.7, especially in the case of cellulose acetate. It is expedient if the cellulose ester, in particular cellulose acetate, with respect to an advantageous degree of polymerization with respect to the average degree of polymerization Solution of the task is optimized. The optimum average degree of polymerization is between 150 and 500, in particular between 180 and 280 in the cellulosic ester.
Die erfindungsgemäßen Kunststoffe, insbesondere  The plastics according to the invention, in particular
Cellulo Seesterzusammensetzungen lassen sich mit hoher Geschwindigkeit in der Umwelt katalytisch abbauen. Eine geeignete Messgröße ist, wie die Cellulo starter compositions can be catalytically degraded at high speed in the environment. A suitable measure is, like the
nachfolgenden Beispiele zum Ausdruck bringen, die zeitliche Reduzierung der Masse des katalytisch abbaubaren Kunststoffs. Der Kern der Erfindung liegt also in der Auswahl eines übergangsmetallmodifizierten Titandioxids, das auf seiner Oberfläche oder auch im gesamten Volumen übergangsmetallmodifiziert ist. Bevorzugt wird ein übergangsmetallmodifiziertes Titandioxid, dessen Oberfläche übergangsmetalldotiert ist. Durch die Dotierung wird die Bandlücke des Halbleiters Titandioxid verkleinert und es kann im Vergleich zu undotiertem Titandioxid auch längerwelliges Licht zur Anregung eines Valenzbandelektrons und damit zur Aktivierung der photokatalytischen Eigenschaften genutzt werden. The following examples express the time reduction of the mass of the catalytically degradable plastic. The core of the invention thus lies in the selection of a transition-metal-modified titanium dioxide, which is transition-metal-modified on its surface or else in the entire volume. Preference is given to a transition-metal-modified titanium dioxide whose surface is transition-metal-doped. By doping the band gap of the semiconductor titanium dioxide is reduced and it can be used in comparison to undoped titanium dioxide and longer wavelength light for exciting a valence band electron and thus to activate the photocatalytic properties.
Zweckmäßigerweise wird die Kristallitgröße des übergangsmetalldotierten Titandioxids optimiert, wobei die Kristallitgröße vorzugsweise zwischen 5 und 150 nm, insbesondere zwischen 7 bis 25 nm liegt. Im Einzelfall kann es vorteilhaft oder sogar notwendig sein, ein grobteiliges  The crystallite size of the transition metal-doped titanium dioxide is expediently optimized, the crystallite size preferably being between 5 and 150 nm, in particular between 7 and 25 nm. In individual cases, it may be advantageous or even necessary, a coarse
übergangsmetallmodifiziertes Titandioxid zu mahlen, um die optimale Transition metal modified titanium dioxide to grind to the optimum
Korngröße einzustellen. Zweckmäßigerweise weist das Set grain size. Appropriately, that has
übergangsmetallmodifizierte Titandioxid eine Dichte (ISO 787, Teil 10) von 3,0 bis 5,0 g/cm3 auf, insbesondere von 3,5 bis 4,2 g/cm3 auf. Vorteilhaft wirkt sich auch für einen Abbau des Celluloseester-haltigen Kunststoffs eine Optimierung der spezifischen Oberfläche des übergangsmetallmodifiziertentransition metal modified titanium dioxide has a density (ISO 787, Part 10) of 3.0 to 5.0 g / cm 3 , in particular from 3.5 to 4.2 g / cm 3 . An advantageous effect also for a degradation of the cellulose ester-containing plastic is an optimization of the specific surface of the transition metal-modified
Titandioxids aus. Dabei ist es bevorzugt, wenn die spezifische Oberfläche BET des übergangsmetalldotierten Titandioxids größer als 100 m2/ g, insbesondere größer als 250 m2/g ist. Besonders vorteilhaft wirkt sich die Einbeziehung eines übergangsmetallmodifizierten Titandioxids in den erfindungsgemäßen katalytisch abbaubaren Kunststoff dann aus, wenn das Titanium dioxide. It is preferable that the BET specific surface area of the transition metal-doped titanium dioxide is greater than 100 m2 / g, in particular greater than 250 m 2 / g. The inclusion of a transition-metal-modified titanium dioxide in the catalytically degradable plastic according to the invention has a particularly advantageous effect if the
übergangsmetallmodifizierte Titandioxid mit einer gegenüber reinem Titandioxid erhöhten Lichtabsorption im Bereich von λ > 400 nm gekennzeichnet ist. Transition-metal-modified titanium dioxide is characterized with a compared to pure titanium dioxide increased light absorption in the range of λ> 400 nm.
Um die katalytische Abbaubarkeit des erfindungsgemäßen Kunststoffs weiter zu verbessern, ist es zweckmäßig, dessen Gehalt an  In order to further improve the catalytic degradability of the plastic according to the invention, it is expedient to its content
übergangsmetallmodifiziertem Titandioxid auf 0,1 bis 5 Gew.- %, insbesondere auf 0,3 bis 1,5 Gew.- % einzustellen. Der Übergangsmetallgehalt des übergangsmetallmodifizierten Titandioxids ist nicht wesentlich beschränkt. Vorzugsweise enthält das transition-metal-modified titanium dioxide to 0.1 to 5% by weight, in particular 0.3 to 1.5% by weight. The transition metal content of the transition metal-modified titanium dioxide is not significantly limited. Preferably contains
übergangsmetallmodifizierte Titandioxid Übergangsmetall in einer Menge von 0,05 bis 5 Gew.- %, insbesondere von 0,3 bis 3 Gew.- %. transition metal-modified titanium dioxide transition metal in an amount of 0.05 to 5% by weight, in particular from 0.3 to 3% by weight.
Erfindungsgemäß ist es möglich, dass der katalytisch abbaubare Kunststoff im Wesentlichen nicht allein auf Celluloseestern basiert. Es können übliche Additive wie z.B. Weichmacher, einbezogen sein, so in dem Falle der  According to the invention, it is possible that the catalytically degradable plastic is essentially not based solely on cellulose esters. Conventional additives such as e.g. Plasticizers, be included, so in the case of
Verwendung in Fasern der Filtermaterialien von Zigaretten. Use in fibers of filter materials of cigarettes.
Andererseits kann zusätzlich ein nicht-übergangsmetallmodifiziertes Titandioxid, insbesondere Anatas, in feiner Dispergierung einbezogen sein, dies insbesondere in dem die Zigarettenindustrie betreffenden Anwendungsfall. Um den erfindungsgemäßen Gedanken möglichst weitgehend zu folgen und die besondere photokatalytische Wirksamkeit des übergangsmetallmodifizierten Titandioxids beim Abbau eines Kunststoffs zu nutzen, ist es bevorzugt, dass der Gehalt des katalytisch abbaubaren Kunststoffs an Celluloseester mindestens 60 Gew.- % insbesondere mindestens 90 Gew.- % ausmacht.  On the other hand, in addition, a non-transition-metal-modified titanium dioxide, in particular anatase, may be included in fine dispersion, especially in the case of the cigarette industry. In order to follow the idea according to the invention as much as possible and to utilize the particular photocatalytic activity of the transition-metal-modified titanium dioxide in the degradation of a plastic, it is preferred that the content of the catalytically degradable plastic of cellulose ester is at least 60% by weight, in particular at least 90% by weight ,
Die gute katalytische Abbaubarkeit des erfindungsgemäßen Kunststoffs, erweist sich insbesondere dann, wenn der katalytisch abbaubare Kunststoff in einen Formkörper überführt wird, insbesondere in Fasern, Folien, insbesondere tiefgezogene Folien, vor allem zur Anwendung als Verpackungsmaterialien, von Spritzgussartikeln, dickwandigen Formkörpern, Granulaten, Mikrobeads, Perlen sowie Gefäßen. Besonders vorteilhaft ist daher die Weiterverarbeitung dieser Fasern zu Filtertows, mit denen Filterstäbe und daraus Filterstöpsel von  The good catalytic degradability of the plastic according to the invention, in particular, when the catalytically degradable plastic is converted into a shaped body, especially in fibers, films, especially deep-drawn films, especially for use as packaging materials, injection molded articles, thick-walled moldings, granules, microbeads , Pearls and vessels. Therefore, the further processing of these fibers into filter tows, with which filter rods and filter caps of
Filterzigaretten hergestellt werden. Derartige Filterstöpsel, die sich in der Umwelt finden, werden bedeutend schneller als solche abgebaut, die nicht modifiziertes Titandioxid enthalten. Filter cigarettes are produced. Such filter plugs found in the environment are degraded significantly faster than those containing unmodified titanium dioxide.
Schließlich sei noch angemerkt, dass das Verfahren zur Herstellung des erfindungsgemäßen katalytisch abbaubaren Kunststoffs keinen besonderen Beschränkungen unterliegt. Eine Möglichkeit besteht darin, die  Finally, it should be noted that the method for producing the catalytically degradable plastic according to the invention is not particularly limited. One possibility is the
Einzelbestandteile dadurch zu vermischen, indem der Kunststoff aufgeschmolzen und die relevanten Bestandteile eingemischt werden. Die Herstellung der Fasern erfolgt zweckmäßigerweise nach dem Trockenspinnverfahren, wenngleich das Nassspinnverfahren ebenfalls in Betracht kommen kann. Beim Trockenspinnverfahren wird der Kunststoff, insbesondere Celluloseester vorzugsweise in üblicher Weise, beispielsweise in Aceton, aufgelöst. Dann werden die relevanten weiteren Bestandteile, wie insbesondere das übergangsmetallmodifizierte Titandioxid hinzugegeben, um dann in einem Trocknungskanal den üblichen Spinnvorgang vorzunehmen. Eine andere Ausführungsform des Trockenspinnverfahrens sieht vor, die relevanten weiteren Bestandteile - außer dem Kunststoff, insbesondere Celluloseester - wie insbesondere das übergangsmetallmodifizierte Titandioxid, mit einem geeigneten Lösungsmittel, beispielsweise Aceton, zu mischen und dann den Kunststoff, insbesondere Celluloseester, hinzuzugeben. Auch diese Mischung wird dann in einem Trocknungskanal für den üblichen Spinnvorgang verwendet. To mix individual constituents by melting the plastic and mixing in the relevant ingredients. The production of the fibers is expediently carried out by the dry spinning process, although the wet spinning process may also be considered. In the dry-spinning process, the plastic, in particular cellulose ester, is preferably dissolved in the customary manner, for example in acetone. Then the relevant other ingredients, such as the particular Transition metal modified titanium dioxide added to then perform the usual spinning in a drying channel. Another embodiment of the dry-spinning process envisages mixing the relevant further constituents-apart from the plastic, in particular cellulose ester-in particular the transition metal-modified titanium dioxide, with a suitable solvent, for example acetone, and then adding the plastic, in particular cellulose ester. This mixture is then used in a drying channel for the usual spinning process.
Sollte der Inhalt jedweder Patente, Patentanmeldungen und  Should the content of any patents, patent applications and
Veröffentlichungen, auf die in dieser Anmeldung Bezug genommen wird, mit dem Inhalt der vorliegenden Anmeldung kollidieren insofern, als dass die Kollision eine Definition der vorliegenden Anmeldung unklar erscheinen lässt, so hat die vorliegenden Anmeldung Vorrang. Publications referred to in this application conflict with the content of the present application in that the collision makes a definition of the present application unclear, so the present application has priority.
Die Erfindung wird nachfolgend anhand von Beispielen noch näher erläutert :  The invention will be explained in more detail below with reference to examples:
Beispiel 1 example 1
Ein gemäß Beispiel 2 der WO 2012/139726 hergestelltes  A manufactured according to Example 2 of WO 2012/139726
eisenmodifiziertes Ti02 wird gemäß dem in Beispiel 1 der WO 2010/017989 offenbarten Verfahren bei der Herstellung eines Celluloseacetat basierenden Filterstabes verwendet. Der erfindungsgemäße Filterstab zeigt eine im Vergleich zu einem mit nicht modifiziertem Ti02 hergestellten Filterstab eine verbesserte Abbaubarkeit unter Umweltbedingungen. Iron-modified TiO 2 is used according to the method disclosed in Example 1 of WO 2010/017989 in the production of a cellulose acetate-based filter rod. The filter rod of the present invention exhibits improved degradability under environmental conditions compared to a filter rod made with unmodified TiO 2.

Claims

P A T E N T A N S P R U C H E PATENT CLAIMS
1. Katalytisch abbaubarer Kunststoff, insbesondere photokatalytisch abbaubarer Kunststoff, dadurch gekennzeichnet, dass der katalytisch abbaubare Kunststoff ein katalytisch wirksames durch Zusatz mindestens eines 1. catalytically degradable plastic, in particular photocatalytically degradable plastic, characterized in that the catalytically degradable plastic catalytically effective by adding at least one
Übergangsmetalles, insbesondere Eisen, modifiziertes Titandioxid enthält. Transition metal, in particular iron, modified titanium dioxide contains.
2. Katalytisch abbaubarer Kunststoff nach Anspruch 1, dadurch gekennzeichnet, dass der Kunststoff einen Cellulo Seester, insbesondere 2. catalytically degradable plastic according to claim 1, characterized in that the plastic is a cellulosic ester, in particular
Celluloseacetat, Cellulosepropionat, Cellulosebutyrat, Celluloseacetatpropionat und/oder Celluloseacetatbutyrat darstellt. Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate and / or cellulose acetate butyrate.
3. Katalytisch abbaubarer Kunststoff nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Celluloseester, insbesondere Celluloseacetat, einen durchschnittlichen Substitutionsgrad (DS) von 1,5 bis 3,0, insbesondere 3. catalytically degradable plastic according to claim 1 or 2, characterized in that the cellulose ester, in particular cellulose acetate, an average degree of substitution (DS) of 1.5 to 3.0, in particular
2,2 bis 2,7, aufweist.  2.2 to 2.7, has.
4. Katalytisch abbaubarer Kunststoff nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Celluloseester, insbesondere Celluloseacetat, einen durchschnittlichen Polymerisationsgrad von 150 bis 500, insbesondere von 180 bis 280 aufweist. 4. Catalytically degradable plastic according to one of claims 1 to 3, characterized in that the cellulose ester, in particular cellulose acetate, has an average degree of polymerization of 150 to 500, in particular from 180 to 280.
5. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass er zusätzlich in feiner Dispergierung ein nicht-übergangsmetallmodifiziertes Titandioxid enthält, insbesondere Anatas. 5. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that it additionally contains, in fine dispersion, a non-transition-metal-modified titanium dioxide, in particular anatase.
6. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 6. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the
übergangsmetallmodifizierte Titandioxid auf seiner Oberfläche Transition-modified titanium dioxide on its surface
übergangsmetalldotiert ist. Transition metal is doped.
7. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 7. catalytically degradable plastic according to at least one of the preceding claims, characterized in that the
übergangsmetallmodifizierte Titandioxid eine Kristallitgröße von 5 bis 150 nm, insbesondere von 7 bis 25 nm aufweist. Transition-metal-modified titanium dioxide has a crystallite size of 5 to 150 nm, in particular from 7 to 25 nm.
8. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 8. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the
übergangsmetallmodifizierte Titandioxid eine Dichte (ISO 787, Teil 10) von 3,0 bis 5,0 g/cm3, insbesondere von 3,5 bis 4,2 g/cm3 aufweist. transition metal modified titanium dioxide has a density (ISO 787, Part 10) of 3.0 to 5.0 g / cm 3 , in particular from 3.5 to 4.2 g / cm 3 .
9. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die spezifische Oberfläche (nach BET) des übergangsmetallmodifizierten Titandioxids größer als 100 m2/g, insbesondere größer als 250 m2/g ist. 9. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the specific surface area (according to BET) of the transition metal-modified titanium dioxide is greater than 100 m 2 / g, in particular greater than 250 m 2 / g.
10. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 10. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the
übergangsmetallmodifizierte Titandioxid mit einer gegenüber reinem Titandioxid erhöhten Lichtabsorption im Bereich von λ > 400 nm gekennzeichnet ist. Transition-metal-modified titanium dioxide is characterized with a compared to pure titanium dioxide increased light absorption in the range of λ> 400 nm.
11. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der katalytisch abbaubare Kunststoff 0,1 bis 5 Gew.- %, insbesondere 0,3 bis 1,5 Gew.- % übergangsmetalldotiertes Titandioxid enthält. 11. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the catalytically degradable plastic contains 0.1 to 5% by weight, in particular 0.3 to 1.5% by weight of transition metal-doped titanium dioxide.
12. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 12. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the
übergangsmetallmodifizierte Titandioxid einen Übergangsmetallgehalt von 0,05 bis 5 Gew.- %, insbesondere von 0,3 bis 3 Gew.- % aufweist. Transition-metal-modified titanium dioxide has a transition metal content of 0.05 to 5% by weight, in particular from 0.3 to 3% by weight.
13. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Gehalt an 13. Catalytically degradable plastic according to at least one of the preceding claims, characterized in that the content of
Cellulo Seester mindestens 60 Gew.- %, insbesondere 90 Gew.- % ausmacht. Cellulo Seester at least 60% by weight, in particular 90% by weight.
14. Katalytisch abbaubarer Kunststoff nach mindestens einem der vorhergehenden Ansprüche als Formköper, insbesondere in Form von Fasern, insbesondere Fasern, die Bestandteile eines Filtertow sind, Folien, insbesondere tiefgezogenen Folien, insbesondere zur Anwendung als Verpackungsmaterialien, von Spritzgussartikeln, dickwandigen Formkörpern, Granulaten, Mikrobeads, Perlen sowie Gefäßen. 14. Catalytically degradable plastic according to at least one of the preceding claims as shaped bodies, in particular in the form of fibers, in particular fibers which are components of a filter tow, films, in particular thermoformed films, in particular for use as packaging materials, injection molded articles, thick-walled moldings, granules, microbeads , Pearls and vessels.
15. Verwendung des katalytisch abbaubaren Kunststoffs nach 15. Use of the catalytically degradable plastic after
Anspruch 14, dadurch gekennzeichnet, dass das Filtertow zur Herstellung von Filterstöpseln von Zigarettenfiltern herangezogen wird. Claim 14, characterized in that the filter tow is used for the production of filter plugs of cigarette filters.
EP14744596.9A 2013-08-12 2014-07-30 Catalytically degradable plastic and use of same Withdrawn EP3032972A1 (en)

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