WO2012088585A1 - Additifs oxo-biodégradables destinés à être utilisés dans des films polymères combustibles fossiles et un emballage à usage unique - Google Patents

Additifs oxo-biodégradables destinés à être utilisés dans des films polymères combustibles fossiles et un emballage à usage unique Download PDF

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WO2012088585A1
WO2012088585A1 PCT/CA2011/001385 CA2011001385W WO2012088585A1 WO 2012088585 A1 WO2012088585 A1 WO 2012088585A1 CA 2011001385 W CA2011001385 W CA 2011001385W WO 2012088585 A1 WO2012088585 A1 WO 2012088585A1
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Prior art keywords
polymer
composition
oxo
film
composition according
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PCT/CA2011/001385
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English (en)
Inventor
Aman Ur Rahman
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Enerplastics Llc
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Priority to CA2821357A priority Critical patent/CA2821357C/fr
Priority to TW100149338A priority patent/TW201237087A/zh
Publication of WO2012088585A1 publication Critical patent/WO2012088585A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • the invention broadly falls in the technical field of Chemistry. More particularly the present invention is in the technical field of Oxo- biodegradability of fossil fuel polymers. More specifically the invention relates to chemical compounds used in defined percentage composition to achieve Oxo-biodegradability of polyolefins such as polyethylene and polypropylene, as defined by a unique predictive 'pass-fail' criterion set out in accelerated laboratory testing procedures by France's leading Research Institutes-CNEP and SEESIB.
  • polyolefins such as polyethylene and polypropylene
  • ASTM 6954 Standard Guide for exposing and Testing Plastics that Degrade in the Environment by a Combination of Oxidation and Biodegradation
  • ASTM 6954 itself states that it addresses test methods and procedures and is thus only a guideline recommended for comparative study for polymer performance on Oxo-biodegradation and therefore does not provide a pass/fail criterion or product specification for Oxo-biodegradability of products.
  • a similar standard has been adopted by the British Standards Institute, BSI earlier this year. (BS 8472:2011 - Methods for the assessment of the oxo-biodegradation of plastics and of the phyto-toxicity of the residues in controlled Laboratory conditions.)
  • Oxidation and biodegradation of polyethylene films containing pro-oxidant additives Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation; Polymer degradation and Stability 95 (2010) 1 106-1 1 14, herein incorporated by reference.
  • the present disclosure provides compositions and information relating to a balanced recipe of pro and anti oxidant additives, for use in polymer films and packaging material.
  • the disclosure provides compositions that predict the final product to qualify as Oxo- biodegradable under scientifically based 'Pass-Fail' test protocols in an effort to solve the issue of certifiable Oxo-biodegradability when compared to self- claimed Oxo-biodegradable products in the markets.
  • the disclosure provides chemical compounds which when added in defined percentage to conventional fossil fuel based polymers accelerate their degradation process after a pre-established 'in-use' life.
  • the end-user product (a polymer to which the developed additive or composition is added at a recommended dosage) containing one or more of the chemical components is then subjected to predictive test protocols developed by Centre National d' Evaluation de Photo protection (CNEP) and Synthese et Etude des Systemes a Interet Bitechnik (SEESIB), which would guarantee a desired service life at full mechanical properties; thereafter to fragment within a few months and subsequently to oxo-biodegrade in a 2-3 years span, on exposure to normal environmental conditions.
  • CNEP Centre National d' Evaluation de Photo protection
  • SEESIB Synthese et Etude des Systemes a Interet Bitechnik
  • the CNEP/SEESIB's testing protocol based on macro-molecular considerations, is currently the only accelerated pass/fail protocol where laboratory results are reflective of actual environmental conditions and bio- assimilation time frame; established by them over a two decade study of actual environmental behavior versus accelerated laboratory testing, measuring and predicting such behavior.
  • a composition comprising i) a pro-oxidant comprising one or more organo-metallic stearates selected from iron, manganese and cobalt; ii) one or more phenolic antioxidants; iii) a polymer base; and iv) an inert filler.
  • the composition is master batch or an additive master batch.
  • the master batch is a solid.
  • the master batch is useful for imparting properties to plastics, such as polymer based plastics.
  • the composition comprises a polymer base.
  • the polymer base is a polyolefin, such as polyethylene or polypropylene.
  • the composition comprises a pro-oxidant such as organo-metallic stearates of Iron, Manganese and Cobalt.
  • organo-metallic stearates refers to compounds having the formula (Ci 8 H 3 5COO " ) 2 X, where X can be iron, cobalt or manganese.
  • the pro-oxidant consists of metallic stearates of Iron, Manganese and Cobalt.
  • the pro-oxidant comprises from about 15 to about 30 percent by weight of the total composition.
  • the composition comprises a phenolic antioxidant.
  • suitable phenolic antioxidants for use with the composition described herein are marketed under trade names IRGANOX 1010; RICHNOX 1010 and EVERNOX-10.
  • the phenolic anti-oxidant has the chemical formula of C, , , ⁇ ,,.
  • the phenolic antioxidant comprises from about 10 to about 20 percent by weight of the total composition.
  • compositions provided herein include one or more inert fillers.
  • the inert filler is Calcium carbonate and/or Titanium Dioxide.
  • the present disclosure includes articles made using the compositions described herein.
  • one embodiment includes polymer-based film or containers suitable for use as packaging prepared by diluting the compositions described herein.
  • the polymer- based film or containers suitable for use as packaging are made by diluting the compositions, such as a master batch, to about 1 - 5 percent into a polymer resin.
  • the polymer resin is a polyolefin carrier resin.
  • the articles made using the compositions described herein are Oxo-biodegradable products which meet the requirements of CNEP/SEESIB protocols.
  • the polymer-based film or container is an Oxo-biodegradable product which meets the requirements of CNEP/SEESIB protocols.
  • compositions and articles described herein include colour pigments and/or other additives known to a person of skill in the art.
  • polymer-based films or containers used for any kind of packaging/carriage materials comprising the composition described herein.
  • compositions described herein comprising mixing a pro-oxidant with one or more phenolic antioxidants, a polymer base and an inert filler. Also provided are methods for producing an oxo-biodegradable product, such as a polymer-based film or container, comprising diluting the compositions described herein with a polymer base.
  • One aspect of the disclosure is a recipe for an oxo- biodegradable (OBD) master batch, consisting of 15 to 30 percent by weight of a mix of organo-metallic stearates of Iron, Manganese and Cobalt, along with a phenolic antioxidant at 10 to 20 percent with the balance being a pure polymer with an inert filler like calcium carbonate and/or Titanium Dioxide.
  • OBD oxo- biodegradable
  • Another aspect of the disclosure is to prepare and submit articles, such as films/ disposable food trays etc., identical to those in actual everyday use by consumers, for testing under the CNEP/SEESIB protocols, in a shape and form as near to the actual article used by consumers in the market place (which ensures that the final product will behave as predicted in the accelerated lab tests under the protocols.).
  • Figure 1 shows 55 ⁇ EP OBD-2 film thermo-oxidized at 60 degrees Celsius characterized using FTIR for up to 425 hours.
  • Figure 2 shows 55 pm EP OBD-2 film thermo-oxidized at 60 degrees Celsius characterized using FTIR for up to 425 hours.
  • Figure 3 shows absorbance at 1719 cm-1 as a function of time (duration) for EPOBD2 samples.
  • Figure 4 shows FTIR of EP OBD-2 film exposed under SEPAP12/24 (60 degrees Celsius) conditions for up to 100 hours.
  • Figure 5 shows FTIR of EP OBD-2 film exposed under SEPAP12/24 (60 degrees Celsius) conditions for up to 100 hours. Absorbance at 1719 cm-1 generally increases with the duration of treatment.
  • Figure 6 shows FTIR of samples of film containing EP OBD-2 pre-exposed in SEPAP 12/24 for 20 hours, and thermo-oxidized at 60 degrees Celsius in the aerated oven.
  • Figures 7 shows FTIR of samples of film containing EP OBD-2 pre-exposed in SEPAP 12/24 for 20 hours, and thermo-oxidized at 60 degrees Celsius in the aerated oven. Absorbance at 1719 cm-1 increase with the duration of thermo-oxidation.
  • Figure 8 shows FTIR characterizing the chemical evolution of EP OBD-2 film after 70 hours of exposure in SEPAP 12/24 until fragmentation, after 96 hours of thermo-oxidation and the initial state of the film.
  • Figure 9 shows FTIR characterizing the chemical evolution of EP OBD-2 film after 70 hours of exposure in SEPAP 12/24 until fragmentation, after 96 hours of thermo-oxidation and the initial state of the film. Absorbance at 1715 cm-1 is highest in the 96h E60C sample, followed by 70h SEPAP while the initial sample shows only a relatively small absorbance at -1715 cm-1.
  • Figure 10 shows variations of the ATP concentration expressed in p mol/ml vs. the biotest duration.
  • Figure 1 1 shows a general chemical reaction for polyethylene degradation in the presence of organic salts of transition metals.
  • the recipe is for an Oxo-biodegradable (OBD) master batch, consisting of 15 to 30 percent by weight of a mix of organo-metallic stearates of Iron, Manganese and Cobalt along with 10 - 20 percent phenolic antioxidant with the balance being a pure polymer along with an inert filler like calcium carbonate and/or Titanium Dioxide, which will ensure in-use mechanical integrity of 1 year.
  • OBD Oxo-biodegradable
  • the aforementioned OBD master batch is then diluted between 1-5 percent into the same polyolefin polymers. This process facilitates the replication of samples, such as films/ disposable food trays etc for end-use in thickness and weight.
  • the final sample which resembles the actual article used by consumers in the market place, may then be subjected to the accelerated lab tests under the protocols.
  • the final sample is termed as EP OBD2 (trade name).
  • composition comprising: i) a pro-oxidant comprising one or more organo-metallic stearates selected from iron, manganese and cobalt; ii) one or more phenolic antioxidants; iii) a polymer base; and iv) an inert filler.
  • a pro-oxidant comprising one or more organo-metallic stearates selected from iron, manganese and cobalt
  • ii) one or more phenolic antioxidants iii) a polymer base
  • the composition comprises a pro-oxidant consisting of organo-metallic stearates selected from iron, manganese and cobalt.
  • the composition comprises a polymer base such as a polyolefin.
  • the polyolefin is polyethylene.
  • the polyolefin is polypropylene.
  • the composition comprises a pro-oxidant comprising metallic stearates of Iron, Manganese and Cobalt from about 15 to about 30 percent by weight of the total composition.
  • the composition comprises a phenolic antioxidant from about 10 to about 20 percent by weight of the total composition.
  • the composition includes an inert filler such as calcium carbonate and/or titanium dioxide.
  • a polymer-based film or container suitable for use as packaging prepared by diluting a composition described herein from 1 to about 5 percent into a polyolefin carrier resin.
  • the polymer-based film or container is an Oxo-biodegradable product which meets the requirements of CNEP/SEESIB protocols.
  • compositions described herein may also include colour pigments and/or other additives.
  • polymer-based film or container described may also include colour pigments and/or other additives.
  • a polymer-based film or container used for any kind of packaging/carriage materials comprising the composition described herein.
  • the incident light emitted by 4 medium pressure mercury arcs and filtered by the borosilicate envelope of the 4 lamps does not contain any wavelength shorter than 290 nm ;
  • the temperature of the exposed surface is controlled and maintained at (60 ⁇ 1)°C. -no external water is allowed to come into contact with the exposed sample. However, internal water is formed in the matrix through the decomposition of primary hydro-peroxides.
  • the film After an exposure of 150 hours, the film needs to demonstrate an absorbance increase equal or higher than (x/100) in an FTIR operating in the transmission mode. Achieving this level confirms that the film will fragment within 3 to 4 months after the completion of its in-use life.
  • the SEPAP 12/24 pre-exposed film is then exposed to thermo oxidation at 60°C in an aerated oven for 300 hours.
  • the film should demonstrate an increase in absorbance equal to or higher than 2x/100 when examined in an FTIR run in the transmission mode.
  • the abiotic protocols require that for a film to be considered Oxo-biodegradable i.e. meet the 'pass/fail' criterion for Oxo- biodegradation, it (a), should not oxidize and the absorbance should not be more than (x/1000) (b). be oxidized to an extent equal to (x/100) (exposure to daylight) + (2x/100) (soil thermo oxidation) + (3x/100) to acquire biodegradability.
  • the sample needs to be uniform and of a smaller particle size.
  • the already highly fragmented and very fragile film from step B (a) above are pressed through a sieve with hole diameters about 1 mm.
  • a conventional mineral medium of a composition given in the Biotic Protocols need to be followed.
  • the powdered specimen is then placed in several glass vials and flasks in measured quantities, along with specified volumes of the liquid medium, to which is added defined amount of microorganism or spores and allowed to incubate under specified temperature and controlled agitation, and the incubation is allowed to proceed for 180 days.
  • EP OBD-2 film exposed in experimental conditions of SEPAP 12/24, temperature of exposed surface 60°C, no external water brought on the exposed samples. The film was exposed for 100 hours and chemical evolution was characterized with FTIR during 0, 10, 20,40,60,80, and 100 hours. After 100 hours of exposure the absorbance increase were: (see Figures 4, 5 and 3)
  • the biotest included in the CNEP-SEESIB protocol was carried out on the oxidized particles prepared from the film EP OBD2 through preexposure in SEPAP 12/24 for 70 hours (until fragmentation) and the fragments thermo-oxidized for 96 hours at 60°C.
  • See Figures 8 & 9 present the FTIR spectra which characterized the chemical evolution of EP OBD2 film after 70 hours of exposure in SEPAP 12/24, until fragmentation (red spectrum) and after 96 hours of thermo oxidation of the photo-oxidized fragments (green spectra).
  • the blue spectrum characterized the initial state of (EP OBD2) film whose thickness was 55 pm.
  • the absorbance increases at 1715 cm “1 were respectively 1.35 after exposure in SEPAP 12/24 and 2.00 after 96 hours of thermo-oxidation at 60°C.
  • the oxidation particles were stored in sterile vials at 4°C.
  • the black plot illustrates the variation of the ATP concentration (i.e. of the population of active cells) in the medium in which the oxidized polymer particles were added.
  • the dotted red plot illustrates the variation of the ATP concentration in the medium in which no oxidized polymer particles were added.
  • the dotted plot evidenced the fact that no increase in the cell population was observed, the initial population of cell being around 10 4 cells per each ml of solution.
  • EP OBD-2 fully oxo-biodegradable under the CNEP/SEESIB protocols for Oxo-biodegradability and fully qualifies for being designated as an OBD product.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

La présente invention concerne un additif d'oxo-biodégradation (OBD), constitué de plusieurs composés chimiques, qui lorsqu'il est ajouté à des polymères plastiques (tels que le polyéthylène ou le polypropylène), leur confère une propriété leur permettant de se fragmenter et de devenir bio-assimilables après un cycle de vie d'utilisation programmé, lorsqu'ils sont exposés aux rayons du soleil et à la chaleur dans l'environnement naturel. Le produit final, c'est-à-dire le produit pour l'utilisateur final, peut être certifiable conformément aux protocoles relatifs à l'oxo-biodégradabilité du CNEP/SEESIB ou à une norme internationale équivalente avec un critère de réussite/échec, pour pouvoir être considéré comme un produit OBD. Les composés de la présente invention utilisés avec des polymères tels que les polyoléfines comprennent des stéarates de métaux de transition tels que le manganèse, le fer et le cobalt en combinaisons variables conjointement avec du carbone de calcium et/ou du dioxyde de titane complété avec un antioxydant phénolique pour garantir une vie utile d'une durée spécifiée. Eventuellement, les compositions de la présente invention ne nécessitent pas l'utilisation d'une quelconque substance d'origine biologique.
PCT/CA2011/001385 2010-12-30 2011-12-20 Additifs oxo-biodégradables destinés à être utilisés dans des films polymères combustibles fossiles et un emballage à usage unique WO2012088585A1 (fr)

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CA2821357A CA2821357C (fr) 2010-12-30 2011-12-20 Additifs oxo-biodegradables destines a etre utilises dans des films polymeres combustibles fossiles et un emballage a usage unique
TW100149338A TW201237087A (en) 2010-12-30 2011-12-28 Oxo-biodegradable additives for use in fossil fuel polymer films and once-used packaging

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CA2726602 2010-12-30
CA2726602A CA2726602A1 (fr) 2010-12-30 2010-12-30 Additifs oxo-biodegradables a utiliser dans les films de polymeres a base de combustibles fossiles et les emballage deja utilises

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CZ304315B6 (cs) * 2012-12-07 2014-02-26 Polymer Institute Brno, Spol. S R.O. Oxo-degratovatelný polyolefinický materiál
WO2015006560A1 (fr) * 2013-07-12 2015-01-15 Weder, Wanda M., Not Individually But Solely As Trustee Of The Family Trust U/T/A Dated 12/8/1995 Compositions pour causer, augmenter et/ou accélérer l'oxo-biodégradation d'articles et leurs procédés de production et leur utilisation
FR3043323A1 (fr) * 2015-11-05 2017-05-12 Cleanis Conteneur oxo-biodegradable antimicrobien
WO2018183528A1 (fr) * 2017-03-28 2018-10-04 Concentrx Pharmaceuticals, Inc. Dispositifs et procédés d'administration de médicaments en poudre sèche
WO2018227166A1 (fr) * 2017-06-09 2018-12-13 Hedgehog Group LLC Emballage rigide et souple oxo-dégradable
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US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
US11732203B2 (en) 2017-03-02 2023-08-22 Hydrocarbon Technology & Innovation, Llc Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials

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