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WO2024110622A1 - Composition - Google Patents

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Publication number
WO2024110622A1
WO2024110622A1 PCT/EP2023/082958 EP2023082958W WO2024110622A1 WO 2024110622 A1 WO2024110622 A1 WO 2024110622A1 EP 2023082958 W EP2023082958 W EP 2023082958W WO 2024110622 A1 WO2024110622 A1 WO 2024110622A1
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WO
WIPO (PCT)
Prior art keywords
composition
fatty acid
additive
acid salt
present
Prior art date
Application number
PCT/EP2023/082958
Other languages
English (en)
Inventor
Kok Boon Heh
Churat Tiyapiboonchaiya
Dr Niwat NINGNUEK
Sombat Tannarat
Pisan UAWITHYA
Original Assignee
SCG Chemicals Public Company Limited
Gordon, Kirsteen
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 SCG Chemicals Public Company Limited, Gordon, Kirsteen filed Critical SCG Chemicals Public Company Limited
Publication of WO2024110622A1 publication Critical patent/WO2024110622A1/fr

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Classifications

    • 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
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the present invention relates to a composition
  • a composition comprising: (i) a polyolefin; (ii) a fatty acid salt of a metal selected from Ce, Mn, Al, Mg and mixtures thereof; and (iii) a partially hydrolysed polyvinyl alcohol (PVA) having a degree of hydrolysis of 30-75%mol.
  • the invention also relates to a method for preparing the composition, to the use of the composition as an additive, and to an additive, preferably an additive masterbatch, comprising the composition.
  • the invention further relates to a polymer composition comprising the additive, preferably an additive masterbatch, and a polymer base composition, and to a method of preparing a polymer composition comprising the additive and a polymer base composition.
  • the invention relates to an article comprising the polymer composition, to a method of preparing an article comprising the polymer composition, and to the use of the polymer composition to prepare an article.
  • polymer materials are ubiquitous in modern life. Depending on the particular choice of polymer, polymer materials are able to offer a variety of desirable physical properties, which make them suitable for a wide variety of different applications. Moreover, polymers typically comprise a backbone of strong covalent bonds, making the polymer resistant to degradation. In normal use, this property is beneficial, as it enables the provision of durable articles for use by the consumer.
  • a polymer degradation additive comprises a polymer carrier along with additional ingredients intended to speed up polymer degradation, and may be supplied as a masterbatch.
  • the masterbatch may be blended with a polymer base composition, and the resultant polymer composition may be moulded or extruded to form an article. The presence of the masterbatch in the polymer composition facilitates degradation of the article on disposal.
  • the strong degradation performance described above must be carefully balanced with the physical properties demanded of the polymer composition during normal use of an article.
  • the inclusion of the masterbatch should not compromise mechanical properties - e.g. flexural modulus, tensile modulus, or Izod impact values - relative to those of the polymer base composition alone. This is important so that the polymer composition can continue to perform its intended function, without any substantial decrease in performance which may be noticed by the end-user.
  • the masterbatch should also not too greatly affect the visual appearance of the polymer composition as compared with the polymer base composition alone. This is important to ensure that articles comprising the masterbatch will not appear aesthetically unappealing to the consumer.
  • the masterbatch should also be safe to use, for example displaying low toxicity, and should have a good degree of processability.
  • WO 2018/199494 A1 CN 1241595 A, CN 110467736 A and CN 106883501 A each disclose compositions comprising polyolefin, certain fatty acid metal salts, and polyvinyl alcohol.
  • composition comprising:
  • the present invention provides a method for preparing a composition as hereinbefore described, comprising mixing:
  • PVA polyvinyl alcohol
  • the present invention provides an additive, preferably an additive masterbatch, comprising a composition as hereinbefore described.
  • the present invention provides the use of a composition as hereinbefore described as an additive, preferably an additive masterbatch.
  • the present invention provides a polymer composition comprising:
  • the present invention provides a method for preparing a polymer composition as hereinbefore described, comprising blending an additive, preferably an additive masterbatch, as hereinbefore described with a polymer base composition.
  • the present invention provides an article comprising a polymer composition as hereinbefore described.
  • the present invention provides the use of a polymer composition as hereinbefore described to prepare an article.
  • the present invention provides a method of preparing an article as hereinbefore described, comprising thermoforming, calendaring, moulding and/or extruding a polymer composition as hereinbefore described.
  • polymer degradation additive refers to a composition which improves the degradation properties of a polymer base composition with which it is blended.
  • the compositions of the present invention may be used as polymer degradation additives.
  • additive masterbatch refers to an additive in a form which may be blended with a polymer base composition to form a polymer composition, with the aim of imparting certain desired properties to the resultant polymer composition.
  • the term “polymer base composition” refers to a composition with which an additive or an additive masterbatch is blended to form a polymer composition.
  • the polymer base composition is the main ingredient of the resultant polymer composition by wt%, based on the total weight of the polymer composition.
  • the polymer composition may comprise the polymer base composition in an amount of at least 50 wt%, preferably at least 60 wt% and more preferably at least 90% based on the total weight of the polymer composition.
  • the polymer base composition comprises a polymer as its main ingredient by wt%.
  • the polymer base composition may comprise polymer in an amount of at least 70 wt%, preferably at least 80 wt% and more preferably at least 90% based on the total weight of the polymer composition.
  • Other ingredients optionally present in the polymer base composition are conventional additives (other than polymer degradation additives).
  • polymer composition refers to a composition resulting from the blending of an additive or an additive masterbatch with a polymer base composition.
  • homopolymer refers to a polymer derived from one single species of monomer.
  • copolymer refers to a polymer derived from more than one species of monomer.
  • the term includes block copolymers, random copolymers, and alternating copolymers.
  • partially hydrolysed polyvinyl alcohol is equivalent to the term “partially hydrolysed polyvinyl acetate”. Both refer to a polyvinyl alcohol prepared by hydrolysis of polyvinyl acetate. The extent of hydrolysis is described by the “degree of hydrolysis (DH)”, which denotes the percentage of acetate groups converted to alchol groups
  • polyvinyl acetate refers to a polymer that comprises at least 50 % wt, preferably at least 75 % wt, more preferably at least 85 % wt, yet more preferably at least 90 % wt units derived from vinyl acetate.
  • polyolefin refers to a polymer that comprises at least 50 % wt, preferably at least 75 % wt, more preferably at least 85 % wt, yet more preferably at least 90 % wt units derived from olefin(s).
  • Preferred olefins are ethylene and propene, in particular propene.
  • polypropylene refers to a polymer that comprises at least 50 % wt, preferably at least 75 % wt, more preferably at least 85 % wt, yet more preferably at least 90 % wt units derived from propene.
  • stearate refers to the anion of stearic acid.
  • depolymerisation catalyst refers to a metal salt which catalyses the depolymerisation of a polymer.
  • fatty acid refers to an aliphatic carboxylic acid.
  • biofood refers to a compound which may be consumed by microorganisms and which promotes the proliferation of said microorganisms.
  • polyhydric alcohol refers to an organic compound with one hydroxyl group bonded directly to each carbon atom.
  • hydroxyl acid is equivalent to the term “hydroxy acid” and refers to a compound comprising at least one carboxylic acid group and at least one hydroxyl group.
  • the present invention relates to a composition
  • a composition comprising
  • compositions comprise a fatty acid metal salt of one metal selected from Ce, Mn, Al and Mg.
  • the metal is preferably Ce.
  • the composition comprises a fatty acid metal salt of each of two, more preferably of each of three, still more preferably of each metal selected from Ce, Mn, Al, and Mg.
  • the composition of the present invention is an additive, more preferably an additive masterbatch.
  • the present invention also relates to an additive, more preferably an additive masterbatch, comprising a composition as hereinbefore described and to the use of a composition as hereinbefore described as an additive, more preferably an additive masterbatch.
  • the present invention additionally relates to a polymer composition
  • a polymer composition comprising an additive, more preferably an additive masterbatch, as hereinbefore described and a polymer base composition.
  • composition or the polymer composition of the present invention offers improved degradation performance. This means that articles comprising the composition or the polymer composition more readily degrade, including following UV- accelerated weathering and/or light exposure.
  • the mechanical and visual properties of the composition or the polymer composition of the present invention do not differ significantly from the mechanical properties of the polyolefin which does not comprise the fatty acid salt of metal and the partially hydrolysed PVA, or a polymer base composition which does not comprise the additive or the additive masterbatch of the present invention, respectively.
  • the flexural modulus, tensile modulus, Izod impact value, and haze value of the composition or the polymer composition of the present invention are not significantly different from those of the polyolefin which does not comprise the fatty acid salt of metal and the partially hydrolysed PVA, or a polymer base composition which does not comprise the additive or the additive masterbatch of the present invention, respectively.
  • the partially hydrolysed PVA used in the composition or the polymer composition of the present invention exhibits lower toxicity, improving its ability to recruit microorganisms, as well as improving the safety of the composition or the polymer composition.
  • the partially hydrolysed PVA used in the composition or the polymer composition of the present invention also contributes to an improved degree of processability.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a polyolefin.
  • the composition, preferably an additive, more preferably an additive masterbatch may comprise multiple polyolefins.
  • the composition, preferably an additive, more preferably an additive masterbatch may comprise two, three, or more polyolefins.
  • the composition of the present invention comprises a single polyolefin.
  • the polyolefin of the present invention may be a copolymer, for example a bipolymer, a terpolymer, or a quaterpolymer.
  • the polyolefin of the present invention is a homopolymer.
  • the polyolefin is selected from a polyolefin comprising monomers derived from a C2-C12 olefin, more preferably a C2-C8 olefin. Still more preferably, the polyolefin is selected from a polyethylene (e.g. a high density polyethylene or a low density polyethylene) or a polypropylene. Most preferably, the polyolefin is polypropylene.
  • the polyolefin is in the form of a powder or particles.
  • the polyolefin of the present invention has an M w of 100,000 to 600,000, more preferably 200,000 to 500,000, still more preferably 300,000 to 400,000.
  • the polyolefin of the present invention has an M n of 10,000 to 80,000, more preferably 30,000 to 60,000, still more preferably 40,000 to 50,000.
  • the polyolefin of the present invention has an M z of 600,000 to 1 ,750,000, more preferably 800,000 to 1 ,500,000, still more preferably 1 ,000,000 to 1 ,300,000.
  • the polyolefin, more preferably polypropylene, of the present invention has a melt flow rate (MFR) 2 to 65 g/10 min at loading 2.16 kg at 230 °C, more preferably 2 to 25 g/10 min, still more preferably about 2 to 12 g/10 min, most preferably 12 g/10 min.
  • the polyolefin, more preferably polypropylene, of the present invention preferably has a melt flow rate (MFR) of 50 to 60 g/10 min at loading 2.16 kg at 230 °C or a melt flow rate (MFR) of 2 to 5 g/10 min at loading 2.16 kg at 230 °C.
  • the polyolefin, more preferably polyethylene, of the present invention has a melt flow rate (MFR) 0.5 to 20 g/10 min at loading 2.16 kg at 190 °C, more preferably 0.5 to 15 g/10 min, still more preferably about 0.6 to 10 g/10 min, most preferably 0.6 to 4 g/10 min.
  • MFR melt flow rate
  • MFR may be measured according to ASTM D 1238 (Year 2020).
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention preferably comprises 30 to 85 wt% polyolefin, more preferably 30 to 75 wt% polyolefin, still more preferably 30 to 60 wt% polyolefin, based on the total weight of the composition.
  • the polyolefin is the main ingredient of the composition, preferably an additive, more preferably an additive masterbatch, by wt%, based on the total weight of the composition.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention preferably comprises 50 to 90 wt% polyolefin, more preferably 59 to 75 wt% polyolefin, based on the total weight of the composition.
  • composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of a metal selected from Ce, Mn, Al, Mg and mixtures thereof.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises one or more of: a fatty acid salt of Ce; a fatty acid salt of Mn; a fatty acid salt of Al; or a fatty acid salt of Mg.
  • a purpose of this ingredient is to act as a depolymerisation catalyst.
  • a depolymerisation catalyst promotes oxidative depolymerisation of a polymer backbone, leading to advantageous levels of polymer degradation in a composition or a polymer composition comprising an additive, preferably an additive masterbatch, of the present invention.
  • the composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of one metal selected from Ce, Mn, Al and Mg.
  • the metal is preferably Ce.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of each of two metals selected from Ce, Mn, Al, and Mg.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention may comprise one or more of the following combinations: a fatty acid salt of Ce and a fatty acid salt of Al; a fatty acid salt of Ce and a fatty acid salt of Mn; a fatty acid salt of Ce and a fatty acid salt of Mg; a fatty acid salt of Mn and a fatty acid salt of Al; a fatty acid salt of Mn and a fatty acid salt of Mg; or a fatty acid salt of Al and a fatty acid salt of Mg.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of each of three metals selected from Ce, Mn, Al, and Mg.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention may comprise one or more of the following combinations: a fatty acid salt of Ce, a fatty acid salt of Mn, and a fatty acid salt of Al; a fatty acid salt of Ce, a fatty acid salt of Al, and a fatty acid salt of Mg; a fatty acid salt of Ce, a fatty acid salt of Mn, and a fatty acid salt of Mg; or a fatty acid salt of Mn, a fatty acid salt of Al, and a fatty acid salt of Mg.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of each of Ce, Mn, Al, and Mg.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention may comprise a fatty acid salt of Ce, a fatty acid salt of Mn, a fatty acid salt of Al, and a fatty acid salt of Mg.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention may comprise multiple (for example two, three, or more) fatty acid salts of metals selected from Ce, Mn, Al, and Mg and mixtures thereof.
  • the composition preferably an additive, more preferably an additive masterbatch, may comprise multiple fatty acids salts of Ce, multiple fatty acid salts of Mn, multiple fatty acid salts of Al, and/or multiple fatty acid salts of Mg.
  • the fatty acid salt may be a salt of an unsaturated fatty acid or of a saturated fatty acid.
  • the fatty acid salt is a salt of a saturated fatty acid.
  • the fatty acid salt is a salt of a C4-28 fatty acid, more preferably a C14-24 fatty acid, still more preferably a C16-20 fatty acid.
  • the fatty acid salt is a salt of a C18 fatty acid.
  • the fatty acid salt is a salt of a fatty acid containing an even number of carbon atoms.
  • the fatty acid salt is a salt of a monocarboxylic fatty acid.
  • the fatty acid salt is a salt of stearic acid.
  • each fatty acid salt may be a salt of the same or of a different fatty acid.
  • each fatty acid salt present in the composition, preferably an additive, more preferably an additive masterbatch, of the present invention is a salt of the same fatty acid.
  • the composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises 5 to 20 wt%, more preferably 7 to 15 wt%, still more preferably 11 to 14 wt% of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Ce
  • the composition preferably an additive, more preferably an additive masterbatch, preferably comprises 0 to 20 wt%, more preferably 0.5 to 12.5 wt%, still more preferably 0.5 to 7.5 wt%, still more preferably 1 to 5 wt%, yet more preferably 1.5 to 3 wt% of a fatty acid salt of Ce, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition may preferably comprise up to 25 wt% of a fatty acid salt of Ce, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mn
  • the composition, preferably an additive, more preferably an additive masterbatch preferably comprises 0 to 20 wt%, more preferably 0.5 to 12.5 wt%, still more preferably 0.5 to 7.5 wt%, still more preferably 1 to 5 wt%, yet more preferably 1.5 to 3 wt% of a fatty acid salt of Mn, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • Another preferred additive more preferably an additive masterbatch, comprises 1 to 15 wt%, more preferably 2 to 10 wt%, still more preferably 3 to 8 wt%, yet more preferably 3 to 7 wt%, especially preferably 3 to 5 wt% of a fatty acid salt of Mn, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Al
  • the composition, preferably an additive, more preferably an additive masterbatch preferably comprises 0 to 20 wt%, more preferably 0.5 to 12.5 wt%, still more preferably 0.5 to 7.5 wt%, still more preferably 1 to 5 wt%, yet more preferably 1.5 to 3 wt% of a fatty acid salt of Al, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mg
  • the composition, preferably an additive, more preferably an additive masterbatch preferably comprises 0 to 20 wt%, more preferably 0.5 to 12.5 wt%, still more preferably 0.5 to 7.5 wt%, still more preferably 1 to 5 wt%, yet more preferably 1.5 to 3 wt% of a fatty acid salt of Mg, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • composition preferably an additive, more preferably an additive masterbatch of the present invention comprises a fatty acid salt of Ce and a fatty acid salt of Al
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Al is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Al is preferably 0.5:1 to 2.2:1 , more preferably 0.6:1 to 2.2:1 , still more preferably 0.7:1 to 2:1 , still more preferably 0.7:1 to 1.8:1 , still more preferably 0.7:1 to 1.5:1 , still more preferably 0.7:1 to 1.3:1 , and still more preferably 0.9:1 to 1.3:1.
  • composition preferably an additive
  • more preferably an additive masterbatch of the present invention comprises a fatty acid salt of Ce and a fatty acid salt of Mg
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mg is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mg is preferably 0.5:1 to 2.2:1 , more preferably 0.6:1 to 2.2:1 , still more preferably 0.7:1 to 2:1 , still more preferably 0.7:1 to 1.8:1 , still more preferably 0.7:1 to 1.5:1 , still more preferably 0.7:1 to 1.3:1 , still more preferably 0.9:1 to 1.3:1.
  • composition preferably an additive
  • more preferably an additive masterbatch of the present invention comprises a fatty acid salt of Mg and a fatty acid salt of Al
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Al is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Al is preferably 0.5:1 to 2.2:1 , more preferably 0.6:1 to 2.2:1 , still more preferably 0.7:1 to 2:1 , still more preferably 0.7:1 to 1.8:1 , still more preferably 0.7:1 to 1.5:1 , still more preferably 0.7:1 to 1.3:1 , still more preferably 0.9:1 to 1.3:1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Ce and a fatty acid salt of Mn
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is preferably 0.1 :1 to 3:0, more preferably 0.1 :1 to 2:1 , still more preferably to 0.1 :1 to 1.5:1 , still more preferably 0.1 :1 to 0.9:1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0, preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Ce and a fatty acid salt of Mn
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is preferably 0.1 :1 to 3:1 , more preferably 0.1 :1 to 2:1 , still more preferably to 0.1 :1 to 1.5:1 , still more preferably 0.1 :1 to 0.9:1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0.1 , preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mg and a fatty acid salt of Mn
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is preferably 0.1 :1 to 2:1 , more preferably to 0.1 :1 to 1.5:1 , still more preferably 0.1 :1 to 0.9:1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0, preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mg and a fatty acid salt of Mn
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is preferably 0.1 :1 to 2: 1 , more preferably to 0.1 : 1 to 1 .5: 1 , still more preferably 0.1 :1 to 0.9: 1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0.1 , preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Al and a fatty acid salt of Mn
  • the weight ratio said fatty acid salt of Al to said fatty acid salt of Mn is preferably 0.1 :1 to 3:0, more preferably 0.1 :1 to 2:1 , still more preferably to 0.1 :1 to 1.5:1 , still more preferably 0.1 :1 to 0.9:1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio said fatty acid salt of Al to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0, preferably to 0.1 : 1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Al and a fatty acid salt of Mn
  • the weight ratio said fatty acid salt of Al to said fatty acid salt of Mn is preferably 0.1 :1 to 3:1 , more preferably 0.1 :1 to 2:1 , still more preferably to 0.1 :1 to 1.5:1 , still more preferably 0.1 :1 to 0.9:1 , still more preferably to 0.3:1 to 0.8:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio said fatty acid salt of Al to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0.1 , preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention also comprises a partially hydrolysed polyvinyl alcohol (PVA) having a degree of hydrolysis of 30-75%mol.
  • PVA polyvinyl alcohol
  • One purpose of the partially hydrolysed polyvinyl alcohol, in combination with any additional biofoods present in the composition, preferably an additive, more preferably an additive masterbatch, is to recruit microorganisms to a polymer base. This enhances biodegradation of a composition or a polymer composition comprising the additive, preferably an additive masterbatch, of the present invention.
  • compositions and polymer compositions comprising the additive, preferably an additive masterbatch, of the present invention leads to improved flexural modulus and/or improved degradation performance, including following UV-accelerated weathering, in compositions and polymer compositions comprising the additive, preferably an additive masterbatch, of the present invention, as compared with comparative compositions and polymer compositions lacking the partially hydrolysed polyvinyl alcohol.
  • the polyvinyl alcohol is a partially hydrolysed polyvinyl alcohol.
  • the degree of hydrolysis is greater than 0%mol and less than 100%mol.
  • the degree of hydrolysis is 30 to 75%mol. It has been found that using a partially hydrolysed polyvinyl alcohol having such a degree of hydrolysis improves the processability of the composition, preferably an additive, more preferably an additive masterbatch, of the present invention.
  • Such a partially hydrolysed polyvinyl alcohol has also been found to have reduced toxicity, making it a superior biofood, as well as improving the safety of the composition, preferably an additive, more preferably an additive masterbatch, of the present invention.
  • the degree of hydrolysis is preferably 35 to 70%mol, still more preferably 35 to 65%mol, and yet more preferably 35 to 50 mol%, e.g. 35 to 45%mol.
  • the degree of hydrolysis is 30 to 65%mol, more preferably 35 to 60%mol, still more preferably 40 to 55%mol and yet more preferably 45 to 55%mol.
  • the degree of hydrolysis is 30 to 55%mol, more preferably 32 to 50mol%, still more preferably 35 to 45 mol% and yet more preferably 38-42 mol%.
  • the composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises 0.1 to 50wt%, more preferably 0.5 to 30 wt%, still more preferably 5 to 25 wt%, yet more preferably 10 to 20 wt% of the partially hydrolysed PVA, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises 0.1 to 60 wt%, more preferably 0.2 to 55 wt%, still more preferably 1 to 25 wt%, yet more preferably 5 to 25 wt% of the partially hydrolysed PVA, e.g. 7.5 to 12.5 wt% based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is 0.2: 1 to 25: 1 , preferably 0.5 : 1 to 10 : 1 , more preferably 0.6 : 1 to 1.5 : 1 , such as 0.6 : 1 to 1.3 : 1.
  • Another preferred weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is 0.6 : 1 to 1.5 : 1.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is preferably 0.1 : 1 to 2: 1 , more preferably 0.1 : 1 to 1 : 1 , still more preferably 0.1 : 1 to 0.7 : 1 , most preferably 0.1 : 1 to 0.3 : 1.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is 0.1 : 1 to 35: 1 , preferably 0.2 : 1 to 30 : 1 , more preferably 0.4 : 1 to 27 : 1.
  • Another preferred weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is 0.1 : 1 to 30: 1 , more preferably 0.2 : 1 to 27 : 1 , still more preferably 0.4 : 1 to 10 : 1 , yet more preferably 0.6 : 1 to 1.5 : 1.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is preferably 0.4 : 1 to 1.75 : 1 , more preferably 0.5 : 1 to 1.5 : 1 , still more preferably 0.5 : 1 to 1.3 : 1.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is preferably 0.2 : 1 to 1.5 : 1 , more preferably 0.3 : 1 to 1 : 1 , still more preferably 0.4 : 1 to 0.75 : 1.
  • the weight ratio of fatty acid salts of metals selected from Ce, Mn, Al, Mg and mixtures thereof to the partially hydrolysed PVA is preferably 0.75 : 1 to 1.75 : 1 , more preferably 1 : 1 to 1.5 : 1 , still more preferably 1.2 : 1 to 1.35 : 1.
  • the weight ratio of fatty acid salts of Ce, preferably Ce stearate, to the partially hydrolysed PVA is 0.05: 1 to 5: 1 , preferably 0.1 : 1 to 2 : 1 , more preferably 0.1 : 1 to 0.75 : 1 , still more preferably 0.1 : 1 to 0.5 : 1 , most preferably 0.12 : 1 to 0.27 : 1.
  • the weight ratio of fatty acid salts of Ce, preferably Ce stearate, to the partially hydrolysed PVA is 0.02: 1 to 7.5: 1 , preferably 0.05 : 1 to 6 : 1 , more preferably 0.07 : 1 to 3 : 1 , still more preferably 0.1 : 1 to 2.5 : 1.
  • the weight ratio of fatty acid salts of Al, preferably Al stearate, to the partially hydrolysed PVA is 0.05: 1 to 5: 1 , preferably 0.1 : 1 to 2 : 1 , more preferably 0.1 : 1 to 0.75 : 1 , still more preferably 0.1 : 1 to 0.5 : 1 , most preferably 0.12 : 1 to 0.27 : 1.
  • the weight ratio of fatty acid salts of Al, preferably Al stearate, to the partially hydrolysed PVA is 0.02: 1 to 7.5: 1 , preferably 0.05 : 1 to 6 : 1 , more preferably 0.07 : 1 to 3 : 1 , still more preferably 0.1 : 1 to 2.5 : 1.
  • the weight ratio of fatty acid salts of Mg, preferably Mg stearate, to the partially hydrolysed PVA is 0.05: 1 to 5: 1 , preferably 0.1 : 1 to 2 : 1 , more preferably 0.1 : 1 to 0.75 : 1 , still more preferably 0.1 : 1 to 0.5 : 1 , most preferably 0.12 : 1 to 0.27 : 1.
  • the weight ratio of fatty acid salts of Mg, preferably Mg stearate, to the partially hydrolysed PVA is 0.02: 1 to 7.5: 1 , preferably 0.05 : 1 to 6 : 1 , more preferably 0.07 : 1 to 3 : 1 , still more preferably 0.1 : 1 to 2.5 : 1.
  • the weight ratio of fatty acid salts of Mn, preferably Mn stearate, to the partially hydrolysed PVA is 0.1 : 1 to 10: 1 , preferably 0.2 : 1 to 4 : 1 , more preferably 0.2 : 1 to 1 : 1 , still more preferably 0.2 : 1 to 0.75 : 1 , most preferably 0.25 : 1 to 0.5 : 1.
  • the weight ratio of fatty acid salts of Mn, preferably Mn stearate, to the partially hydrolysed PVA is preferably 0.05: 1 to 12: 1 , preferably 0.05 : 1 to 6 : 1 , more preferably 0.1 : 1 to 4 : 1 , still more preferably 0.1 : 1 to 0.2 : 1.
  • Another preferred weight ratio of said stearates of Ce, Mn, Al and Mg to the partially hydrolysed PVA is 0.6 : 1 to 1.75 : 1.
  • an additive preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mn and a fatty acid salt of at least one metal selected from Ce, Al, and Mg.
  • weight ratios are as follows.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is 0:1 to 1 :0, more preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Al to said fatty acid salt of Mn is 0:1 to 1 :0, more preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is 0:1 to 1 :0, more preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mn and a fatty acid salt of at least one metal selected from Ce, Al, and Mg
  • weight ratios are as follows.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is 0.1 :1 to 1 :0.1 , more preferably to 0.1 :1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Al to said fatty acid salt of Mn is 0.1 :1 to 1 :0.1 , more preferably to 0.1 : 1 to 0.9:1 , most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is 0.1:1 to 1:0.1, more preferably to 0.1:1 to 0.9:1, most preferably 0.4:1 to 0.7:1.
  • preferred weight ratios are as follows.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is 0.1:1 to 3:0, more preferably 0.1:1 to 2:1, still more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Al to said fatty acid salt of Mn is 0.1:1 to 3:0, more preferably 0.1:1 to 2:1, still more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is 0.1:1 to 2:1, more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of Ce stearate to Mn stearate is 0.1:1 to 1:0.1, more preferably to 0.1:1 to 0.9:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of Al stearate to Mn stearate is 0.1:1 to 1:0.1, more preferably to 0.1:1 to 0.9:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of Mg stearate to Mn stearate is 0.1:1 to 1:0.1, more preferably to 0.1:1 to 0.9:1, most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises Mn stearate and at least one metal stearate selected from Ce stearate, Al stearate and Mg stearate
  • preferred weight ratios are as follows.
  • the weight ratio of said fatty acid salt of Ce to said fatty acid salt of Mn is 0.1:1 to 3:1, more preferably 0.1:1 to 2:1, still more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Al to said fatty acid salt of Mn is 0.1:1 to 3:1, more preferably 0.1:1 to 2:1, still more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the weight ratio of said fatty acid salt of Mg to said fatty acid salt of Mn is 0.1:1 to 2:1, more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3:1 to 0.8:1, most preferably 0.4:1 to 0.7:1.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention preferably also includes a further biofood (e.g. polyhydric alcohol, hydroxy acid) in addition to the partially hydrolysed polyvinyl alcohol hereinbefore described.
  • a further biofood e.g. polyhydric alcohol, hydroxy acid
  • a purpose of the further biofood, in combination with the partially hydrolysed polyvinyl alcohol, is to recruit microorganisms to a polymer base. This enhances biodegradation of a polymer composition comprising the composition of the present invention.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a polyhydric alcohol, preferably a polyhydric alcohol comprising 2 to 24 carbon atoms, more preferably a polyhydric alcohol comprising 2 to 12 carbon atoms, still more preferably a polyhydric alcohol comprising 4 to 6 carbon atoms.
  • Preferred polyhydric alcohols include sorbitol and erythritol.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises sorbitol.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a carboxylic acid, more preferably a hydroxy acid, still more preferably a hydroxy acid comprising 1 to 12 carbon atoms, yet more preferably a hydroxy acid comprising 2 to 10 carbon atoms, most preferably a hydroxy acid comprising 4 to 8 carbon atoms.
  • the carboxylic acid or the hydroxy acid may contain one carboxylic acid group or more than one carboxylic acid group, for example two carboxylic acid groups or three carboxylic acid groups.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention may comprise 1 ,4-cyclohexanedimethanol dibenzoate.
  • the weight ratio of polyhydric alcohol to the partially hydrolysed PVA is preferably 0.05 : 1 to 4 : 1 , more preferably 0.08 : 1 to 2 : 1 , still more preferably 0.10 : 1 to 1.6 : 1 , most preferably 0.10 : 1 to 0.35 : 1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a carboxylic acid, preferably a hydroxy acid
  • the weight ratio of hydroxy acid to the partially hydrolysed PVA is preferably 0.02 : 1 to 4 : 1 , more preferably 0.08 : 1 to 2 : 1 , still more preferably 0.10 : 1 to 1.6 : 1 , most preferably 0.10 : 1 to 0.35 : 1.
  • compositions preferably an additive, more preferably an additive masterbatch, of the present invention may additionally comprise a fatty acid salt of a metal not selected from Ce, Mn, Al, Mg and mixtures thereof.
  • fatty acid salts may be salts of any fatty acid as hereinbefore described.
  • compositions preferably an additive, more preferably an additive masterbatch, of the present invention may comprise a fatty acid salt of Zn.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Zn and a fatty acid salt of Ce
  • the weight ratio of said fatty acid salt of Zn to said fatty acid salt of Ce is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Zn and a fatty acid salt of Al
  • the weight ratio of said fatty acid salt of Zn to said fatty acid salt of Al is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Zn and a fatty acid salt of Mg
  • the weight ratio of said fatty acid salt of Zn to said fatty acid salt of Mg is preferably 3:1 to 1 :3, more preferably 2:1 to 1 :2, still more preferably 1.5:1 to 1 :1.5, most preferably about 1 :1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mn and a fatty acid salt of Zn
  • the weight ratio of said fatty acid salt of Zn to said fatty acid salt of Mn is preferably 0:1 to 1 :0, more preferably 0.2:1 to 1 :0, most preferably about 0.5:1 to 1 :0.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Mn and a fatty acid salt of Zn
  • the weight ratio of said fatty acid salt of Zn to said fatty acid salt of Mn is preferably 0.1 :1 to 1 :0.1 , more preferably 0.2:1 to 1 :1 , most preferably about 0.5:1 to 1 :1.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Zn
  • the composition preferably comprises 0 to 12.5 wt%, more preferably 0.5 to 7.5 wt%, still more preferably about 1 to 5 wt%, yet more preferably 1 .5 to 3 wt% of a fatty acid salt of Zn, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention does not comprise a fatty acid salt of Zn.
  • the composition, preferably an additive, more preferably an additive masterbatch, of the present invention does not comprise Zn. This has the advantage of allowing the composition of the present invention to better meet with regulatory requirements which limit the allowable concentration of Zn.
  • the composition preferably an additive, more preferably an additive masterbatch of the present invention comprises a fatty acid salt of Ca.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention comprises a fatty acid salt of Ca
  • the composition preferably comprises 0 to 12.5 wt%, more preferably 0.25 to 7.5 wt%, still more preferably about 0.5 to 4 wt%, yet more preferably 0.5 to 2.5 wt% of a fatty acid salt of Ca, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • composition preferably an additive, more preferably an additive masterbatch, of the present invention may include a wide variety of additives.
  • additives that are optionally present in the composition of the invention include nucleating agents, dyes, pigments, colour pigments, plasticisers, hardeners, stabilisers, coupling agents, antioxidants, acid scavengers and compatibilizers.
  • Preferred additives include phosphites, including tris(2,4-di-tert- butylphenyl)phosphite, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate), and polypropylene g-Maleic anhydride.
  • the composition of the present invention comprises each of tris(2,4-di-tert- butylphenyl)phosphite, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate), and polypropylene g-Maleic anhydride.
  • any additives present in the composition are preferably present in an amount of 0 to 10 wt%, more preferably 0.25 to 7.5 wt%, still more preferably about 0.5 to 4 wt%, yet more preferably 0.5 to 2.5 wt%, based on the total weight of the composition, preferably an additive, more preferably an additive masterbatch.
  • compositions of the present invention comprise:
  • polyolefin preferably polyethylene or polypropylene
  • a partially hydrolysed polyvinyl alcohol having a degree of hydrolysis of 30-75%mol (iii) a partially hydrolysed polyvinyl alcohol having a degree of hydrolysis of 30-75%mol; and (iv) optionally, a further biofood, preferably selected from a polyhydric alcohol and/or a hydroxy acid.
  • compositions of the present invention comprise
  • polyolefin preferably polyethylene or polypropylene
  • a further biofood preferably selected from a polyhydric alcohol and/or a hydroxy acid.
  • compositions of the present invention comprise:
  • polyolefin preferably polyethylene or polypropylene
  • a further biofood preferably selected from a polyhydric alcohol and/or a hydroxy acid.
  • compositions of the present invention are additives, more preferably additive masterbatches.
  • the present invention provides an additive, preferably an additive masterbatch, comprising of a composition as hereinbefore described.
  • an additive masterbatch comprising of a composition as hereinbefore described.
  • the additive and/or additive masterbatch of the present invention consists of a composition as hereinbefore described.
  • the present invention provides the use of a composition as hereinbefore described as an additive, preferably an additive masterbatch.
  • Preferred additives and additive masterbatches of the present invention are as described above for the compositions of the present invention.
  • Particularly preferred additives and additive masterbatches of the present invention comprise:
  • polyhydric alcohol preferably sorbitol
  • the weight ratio of said combined stearates of Ce, Mn, Al, and Mg to said partially hydrolysed PVA is 0.2: 1 to 25: 1, preferably 0.5 : 1 to 10 : 1, more preferably 0.6 : 1 to 1.75 : 1, still more preferably 0.6 : 1 to 1.5 : 1, most preferably 0.6 : 1 to 1.3 : 1
  • the weight ratio of said polyhydric alcohol to said partially hydrolysed PVA is 0.05 : 1 to 4 : 1, preferably 0.08 : 1 to 2 : 1, more preferably 0.10 : 1 to 1.6 : 1, most preferably 0.10 : 1 to 0.35 : 1
  • the weight ratio of Ce stearate to Mn stearate is 0.1:1 to 3:0, more preferably 0.1:1 to 2:1, still more preferably to 0.1 : 1 to 1.5: 1 , still more preferably 0.1:1 to 0.9: 1 , still more preferably to preferably to
  • polyhydric alcohol preferably sorbitol
  • the weight ratio of said combined stearates of Ce, Mn, Al, and Mg to said partially hydrolysed PVA is 0.2: 1 to 25: 1, preferably 0.5 : 1 to 10 : 1, more preferably 0.6 : 1 to 1.75 : 1, still more preferably 0.6 : 1 to 1.5 : 1, most preferably 0.6 : 1 to 1.3 : 1
  • the weight ratio of said polyhydric alcohol to said partially hydrolysed PVA is 0.05 : 1 to 4 : 1, preferably 0.08 : 1 to 2 : 1, more preferably 0.10 : 1 to 1.6 : 1, most preferably 0.10 : 1 to 0.35 : 1
  • the weight ratio of Ce stearate to Mn stearate is 0.1:1 to 3:1, more preferably 0.1:1 to 2:1, still more preferably to 0.1:1 to 1.5:1, still more preferably 0.1:1 to 0.9:1, still more preferably to 0.3: 1 to 0.8:
  • additives and additive masterbatches of the present invention comprise:
  • polyhydric alcohol preferably sorbitol
  • polyhydric alcohol preferably sorbitol
  • hydroxy acid comprising 4 to 8 carbon atoms
  • the weight ratio of said combined stearates of Ce, Mn, Al, and Mg to said partially hydrolysed PVA is 0.2: 1 to 25: 1 , preferably 0.5 : 1 to 10 : 1 , more preferably 0.6 : 1 to 1.75 : 1 , still more preferably 0.6 : 1 to 1.5 : 1 , most preferably 0.6 : 1 to 1.3 : 1
  • the weight ratio of said polyhydric alcohol to said partially hydrolysed PVA is 0.05 : 1 to 4 : 1 , preferably 0.08 : 1 to 2 : 1 , more preferably 0.10 : 1 to 1.6 : 1 , most preferably 0.10 : 1 to 0.35 : 1
  • the weight ratio of said hydroxy acid to said partially hydrolysed PVA is 0.02 : 1 to 4 : 1 , preferably 0.08 : 1 to 2 : 1
  • the present invention also relates to a method for preparing a composition, an additive, or an additive masterbatch as hereinbefore described, comprising mixing:
  • Preferred methods for preparing the composition, the additive, or the additive masterbatch of the present invention comprise mixing all ingredients in powder form at ambient temperature (e.g. 25 to 45°C) to obtain dry blending.
  • Preferred methods for preparing the composition, the additive, or the additive masterbatch of the present invention further comprise melt mixing the dry blending by using extruder, preferably twin screw extruder, at 190 to 220 °C, then pelletizing and storing the pellets in sealed bag at 25 to 45°C.
  • Preferred methods of the present invention comprise mixing a fatty acid salt of each of two metals selected from Ce, Mn, Al, Mg and mixtures thereof with (i) and (iii).
  • Preferred methods of the present invention comprise mixing a fatty acid salt of each of three metals selected from Ce, Mn, Al, Mg and mixtures thereof with (i) and (iii).
  • Preferred methods of the present invention comprise mixing a fatty acid salt of each of Ce, Mn, Al, and Mg with (i) and (iii).
  • the present invention also relates to a method for preparing a polymer composition as hereinbefore described, comprising blending an additive, preferably an additive masterbatch, as hereinbefore described with a polymer base composition as hereinbefore described.
  • Preferred methods for preparing the polymer composition of the present invention comprise blending all ingredients by physical mixing at ambient temperature and/or extrusion at 190 to 220 °C.
  • the present invention provides a polymer composition.
  • the polymer composition comprises at least two components.
  • the components are:
  • the polymer base composition comprises a polyolefin.
  • the polymer base composition may comprise a copolymer, for example a bipolymer, a terpolymer, or a quaterpolymer.
  • the polymer base composition comprises a homopolymer.
  • the polymer base composition comprises a polyolefin comprising monomers derived from a C2-C12 olefin, more preferably a C2-C8 olefin. Still more preferably, the polymer base composition comprises a polyolefin selected from a polyethylene (e.g. a high density polyethylene or a low density polyethylene) or a polypropylene. Most preferably, the polymer base composition comprises polypropylene.
  • the polymer base composition is in the form of a powder or particles.
  • the polymer base composition has an M w of 100,000 to 600,000, more preferably 200,000 to 500,000, still more preferably 300,000 to 400,000.
  • the polymer base composition has an M n of 10,000 to 80,000, more preferably 30,000 to 60,000, still more preferably 40,000 to 50,000.
  • the polymer base composition has an M z of 600,000 to 1 ,750,000, more preferably 800,000 to 1 ,500,000, still more preferably 1 ,000,000 to 1 ,300,000.
  • the polymer composition of the present invention benefits from a number of advantageous properties.
  • the mechanical and physical properties of the polymer composition do not differ greatly from those of the polymer base composition.
  • the mechanical and physical properties are determined by the methods described in the examples.
  • the polymer composition of the present invention preferably has a tensile modulus of greater than 1200 MPa, more preferably greater than 1400 MPa, still more preferably greater than 1500 MPa.
  • the polymer composition of the present invention preferably has an Izod impact value at 23 °C of greater than 1 .40 KJ/m 2 .
  • the polymer composition of the present invention preferably has a flexural modulus of greater than 1600 MPa, preferably greater than 1700 MPa.
  • the polymer composition of the present invention preferably has a haze value of between 40 to 60.
  • the polymer composition of the present invention preferably exhibits a reduction in a flexural modulus (e.g. tested according to method specified in ISO 19069-2 (2016)) of 0 to 10%, preferably 0 to 5% compared to the polymer composition without the additive hereinbefore described.
  • a flexural modulus e.g. tested according to method specified in ISO 19069-2 (2016)
  • the polymer composition of the present invention also has improved degradation performance, including following UV-accelerated weathering and/or light exposure.
  • the polymer composition of the present invention preferably exhibits a reduction in M w following UV-accelerated weathering (e.g. tested according to method specified in BSI PAS 9017:2020), e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the polymer composition of the present invention preferably exhibits a reduction in M w following light exposure, e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the polymer composition of the present invention combines strong degradation performance with mechanical and visual properties which do not differ significantly from those of the polymer base composition.
  • the polymer composition of the present invention preferably has a flexural modulus of greater than 1600 MPa, preferably greater than 1700 MPa, and exhibits a reduction in M w following UV-accelerated weathering, e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the polymer composition of the present invention more preferably has a flexural modulus of greater than 1600 MPa, preferably greater than 1700 MPa, and exhibits a reduction in M w following light exposure, e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the polymer composition of the present invention comprises 0.1 to 20 wt%, preferably 0.1 to 10 wt%, more preferably 0.5 to 5 wt%, most preferably 1 to 3 wt% of said additive, preferably said additive masterbatch, based on the total weight of polymer composition.
  • the polymer base composition is the main ingredient of the polymer composition by wt%, based on the total weight of the polymer composition.
  • the polymer composition of the present invention comprises 80 to 99.9 wt%, preferably 90 to 99.9 wt%, more preferably 95 to 99.5 wt%, most preferably 97 to 99 wt% of the polymer base composition as hereinbefore described, based on the total weight of the polymer composition.
  • the polymer composition of the present invention consists of an additive, preferably an additive masterbatch, as hereinbefore described and a polymer base composition.
  • the present invention also relates to a method of preparing a polymer composition as hereinbefore described comprising blending an additive, preferably an additive masterbatch as hereinbefore described with a polymer base composition.
  • the present invention also relates to articles comprising a polymer composition as hereinbefore described.
  • Example articles include containers or packaging for food and the like, non-woven and woven products such as wipes, sanitary wear (e.g. diapers), protection gowns, masks (e.g. medical masks), toothbrush bristles, drinking straws, plastic cutlery (e.g. fork, spoon, knife) etc.
  • the articles of the present invention benefit from a number of advantageous properties.
  • the mechanical and physical properties of the article do not differ greatly from articles comprising a polymer base composition and lacking an additive, preferably an additive masterbatch, as hereinbefore described.
  • the articles of the present invention preferably have a tensile modulus of greater than 1200 MPa, more preferably greater than 1400 MPa, still more preferably greater than 1500 MPa.
  • the articles of the present invention preferably have an Izod impact value at 23 °C of greater than 1 .40 kJ/m 2 .
  • the articles of the present invention preferably have a flexural modulus of greater than 1600 MPa, preferably greater than 1700 MPa.
  • the polymer composition of the present invention preferably has a haze value of between 40 to 60.
  • the articles of the present invention preferably exhibit a reduction in a flexural modulus (e.g. tested according to method specified in ISO 19069-2 (2016)) of 0 to 10%, preferably 0 to 5% compared to the article lacking the additive hereinbefore described.
  • the articles of the present invention also have improved degradation performance, including following UV-accelerated weathering and/or light exposure.
  • the articles of the present invention preferably exhibit a reduction in M w following UV-accelerated weathering (e.g. tested according to method specified in BSI PAS 9017:2020), e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the articles of the present invention preferably exhibit a reduction in M w following light exposure, e.g. as described in the examples, of greater than 80%, preferably greater than 90%, most preferably greater than 95%.
  • the articles of the present invention combine strong degradation performance with mechanical and visual properties which do not differ significantly from those of the polymer base composition.
  • the present invention also relates to a method for forming articles comprising conventional polymer processing techniques, such as sheeting/calendering, injection/vacuum/blow/stretch moulding, spunbonding processing, melt blowing/melt stretch processing, and/or extruding a polymer composition as hereinbefore described.
  • the moulding process is selected from an injection moulding process, a blow moulding process, a stretch blow moulding process, a thin wall injection moulding process, or a thermoforming process.
  • the extruding process is selected from a cast film process, or a blow film process.
  • the polymer base composition comprises a polymer having an MFR of 30 to 120 g/10 min, e.g. 50 to 70 g/10 min, more preferably 60-80 g/10 min, e.g. about 60 g/10 min.
  • the polymer base composition comprises a polymer having an MFR of 0.5 to 5.0 g/10 min, e.g. 2 to 5 g/10 min.
  • the polymer base composition comprises a polymer having an MFR of 0.05 to 20 g/10 min, e.g. 10 to 15 g/10 min, more preferably 8 to 12 g/10 min, e.g.
  • the polymer base composition comprises a polymer having an MFR of 10 to 30 g/10 min, more preferably about 12 to 25 g/10 min.
  • the polymer base composition comprises a polymer having an MFR of 500 to 2500 g/10 min, and more preferably about 800 to 1500 g/10 min. MFR may be measured according to A STM D 1238 (Year 2020).
  • the present invention also relates to the use of a polymer composition as hereinbefore described to form an article.
  • Example compositions were prepared as masterbatches.
  • a dry blend of all ingredients was prepared by using a high-speed mixing equipment (Micron Labomixer) at ambient temperature, without heating, for 2-5 mins.
  • the resulting dry blend was subjected to a twin screw extrusion (Thermo Scientific HAAKE TSE or HAAKE TSE16 mm instrument) with the extruder temperature set at 210-220°C, then pelletizing.
  • the resultant composition (masterbatch) in the form of pellets was then stored indoors under ambient temperature (25 to 45 °C, Thailand), well-ventilated conditions in a sealed polypropylene bag.
  • the above masterbatch compositions were blended at 2 wt% with a polypropylene base composition.
  • the blended polymer composition was casted into a film with thickness of 400 micron at a casting condition of 210 °C using a Collins Cast Film Machine.
  • the cast film sample was then cut into a 5 x 5 cm specimen.
  • the above masterbatch compositions were blended at 2 wt% with a polypropylene base composition using a tumbler mixing machine.
  • the pre-blended material was then fed into a Collin Cast Film 7-Layer extruder, with the extruder temperature set between 220-240 °C.
  • the melt polymer from the extruder was casted on the cooling roll, with the cooling roll temperature set at 90°C.
  • the width of the cast film sample was set at 30 cm, which was controlled by the gap of the cutter.
  • the thickness of the cast film sample was kept between 0.15 and 0.2 mm by adjusting the feed rate between 10-15 m/min.
  • This test is a measure of polymer degradation under conditions of UV irradiation.
  • Air chamber temperature 60 °C ( ⁇ 2 °C)
  • Samples were subject to UV-accelerated weathering for a total of 28 days.
  • Carbonyl Index (Cl) (Area under band 1 ,850 - 1 ,650 cm -1 ) I (Area under band 1 ,500 - 1 ,420 cm’ 1 )
  • This test is a measure of polymer degradation under conditions of normal light exposure.
  • Samples were placed inside a glass box with a closed glass lid, size 12 x 24 x 10 inch (WxLxH).
  • the glass box was placed on the building deck in ambient conditions in Thailand during June-August 2021. (Day time temperature and relative humidity are 40- 50°C and 60-80% respectively. Night time temperature and relative humidity are 25-35°C and 60-80% respectively), for 3 months.
  • This test is a measure of different mechanical properties of samples formed from compositions of the present invention.
  • This test is a measure of the aesthetic appearance of samples formed from compositions of the present invention.
  • a Haz BYK Haze instrument was used to measure the haze value of the samples.
  • This test is a measure of the processability of samples formed from compositions of the present invention. This test comprises an assessment of both pellet appearance and cast film appearance. A sample performing well in both tests can be judged to have a good degree of processability.
  • Pellet appearance the appearance of pellets was judged qualitatively by eye for the appearance of any irregularities. If the pellet has a smooth surface with no observed phase separation, all ingredients can be judged to be well compatible, including having good compatibility with the polymer carrier.
  • Cast film appearance the appearance of cast films was judged qualitatively by eye for the appearance of any irregularities. If the cast film has a smooth surface, the masterbatch composition can be judged to be well compatible with the polymer base composition and to have good thermal stability. Surface roughness is indicative of thermal instability and poor compatibility.
  • This test is a measure of the toxicity of different partially hydrolysed polyvinyl acetate ingredients to certain bacteria.
  • the test can thus be used as an indicator of the safety of incorporating such ingredients into compositions of the present invention, as well as their suitability as a biofood.
  • Non-pathogenic Bacillus cereus and non-pathogenic Escherichia coli were obtained for testing from commercial sources.
  • the sample was ground in a centrifugal mill at 12,000 rpm, sieve 0.5 mm
  • %T0 ([Plate count of microbial (CFU/ml) when using blank sample] - [Plate count of microbial (CFU/ml) when using test sample]) x 100 / [Plate count of microbial (CFU/ml) when using blank sample]
  • the samples according to the present invention had a flexural modulus not significantly different from that of the polymer base composition (PO2). This effect was observed across all samples of the present invention, including with different fatty acid salts, biofoods, and ratios of compositional ingredients.
  • CE1 which lacks a partially hydrolysed PVA, showed a relatively lower flexural modulus, which was weakened relative to the polymer base composition (PO2).
  • the samples of the present invention are therefore advantageously better able to be form durable articles which retain a defined shape, as compared with CE1.
  • the samples according to the present invention had a tensile modulus not greatly different from that of the polymer base composition (PO2). This effect was observed across all samples of the present invention, including with different fatty acid salts, biofoods, and ratios of compositional ingredients.
  • the samples according to the present invention retained a high Izod value at room temperature conditions, with the values for each sample not deviating far from that the polymer base composition (PO2). In some cases, the Izod impact value was even improved relative to the polymer base composition.
  • Example 1 show that blending a polymer base composition with 2 wt% of the masterbatch compositions of the present invention does not compromise key mechanical properties, as compared with a polymer base composition alone. This is advantageous as it means that articles comprising such masterbatch compositions retain desirable properties for everyday use.
  • Sample 3 according to the present invention showed a haze value which does not differ greatly from that of the polymer base composition (PO2).
  • Articles comprising masterbatch compositions according to the present invention therefore do not suffer greatly in visual appearance compared to the polymer base composition, meaning such articles remain aesthetically pleasing to the end-user.
  • Samples 1-2 and 5-15 according to the present invention comprising partially hydrolysed PVA having a degree of hydrolysis of 45-55%mol or 38-42%mol showed strong performance in polymer degradation following UV-accelerated weathering.
  • Each of these inventive samples showed a significant percentage decrease in M w as compared with the starting M w .
  • the values of M n and M z following UV-accelerated weathering were also desirably low.
  • the Cl values were also indicative of desirable levels of sample degradation.
  • CE1 which lacks a partially hydrolysed PVA, showed a negligible percentage decrease in M w as compared with the starting M w .
  • M z and M n of CE1 following UV-accelerated weathering were considerably higher than the examples of the present invention.
  • the samples according to the present invention comprising a partially hydrolysed PVA show advantageously improved degradation following UV- accelerated weathering, as compared with CE1 lacking a partially hydrolysed PVA.
  • Samples 2 and 3 according to the present invention each showed strong performance in polymer degradation following light exposure. Each of these inventive samples showed a significant percentage decrease in M w as compared with the starting M w . The values of M n and M z following light exposure were also desirably low.
  • Sample 16 according to the present invention showed strong performance in the processability test.
  • the sample formed a smooth pellet with no observed phase separation. All ingredients were therefore judged to have good compatibility, including with the polymer carrier.
  • the sample also formed a cast film having a smooth surface, leading to the judgment that the masterbatch had good compatibility with the polymer base composition. Taken together, the results led to the conclusion that sample 16 had a good degree of processability.
  • comparative examples 2 and 3 which both lack a partially hydrolysed PVA having a degree of hydrolysis consistent with the compositions of the present invention, both showed inferior performance in the processability test. Both samples produced poor pellets with observed phase separation. Based on this poor performance, the samples were deemed to be unsuitable to be carried forward for cast film appearance testing. This led to the conclusion that the comparative examples had an inferior degree of processability.
  • Example 6 - toxicity
  • Toxicity Sample 1 a partially hydrolysed PVA with a degree of hydrolysis consistent with the compositions of the present invention, showed a desirably low %T0 against both B. cereus and E. Coli.
  • Compositions of the present invention comprising a partially hydrolysed PVA with such a degree of hydrolysis can therefore be considered to have desirably low toxicity, meaning that they, as well as articles comprising the compositions of the present invention, can be considered safe for use.
  • a PVA with such a degree of hydrolysis can also be considered well-suited for use as a biofood.
  • Toxicity Sample 2 which lacks a partially hydrolysed PVA with a degree of hydrolysis consistent with the compositions of the present invention, showed a higher %T0 against both B. cereus and E. Coli., indicating a higher level of toxicity. This indicates that a composition comprising such a partially hydrolysed PVA would offer inferior safety to the user.
  • a PVA with such a degree of hydrolysis can also be considered an inferior biofood.
  • samples comprising the polymer compositions of the present invention pass the criteria set by BSI PAS 9017:2020.
  • Samples comprising the polymer compositions of the present invention also experience minimal impact on mechanical properties and visual appearance, meaning that articles comprising the compositions are suitable for use by the end-user.
  • the samples comprising the polymer compositions of the present invention show superior processability and are judged to have lower toxicity than comparative examples comprising partially hydrolysed PVA with a different degree of hydrolysis. Highly desirable levels of polyolefin degradation, following both UV-accelerated weathering and light exposure, are observed for samples comprising the compositions of the present invention.
  • compositions of the present invention comprising different wt% values and ratios of compositional ingredients, different biofoods, and different catalysts.
  • Degradation following UV-accelerated weathering is significantly inferior when using comparative compositions lacking a partially hydrolysed PVA.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne une composition comprenant : (i) une polyoléfine, (ii) un sel d'acide gras d'un métal choisi parmi Ce, Mn, Al, Mg et des mélanges de ceux-ci, et (iii) un alcool polyvinylique (PVA) partiellement hydrolysé ayant un degré d'hydrolyse de 30 à 75 % en moles, ainsi que des compositions polymères comprenant la composition et une composition de base polymère.
PCT/EP2023/082958 2022-11-25 2023-11-24 Composition WO2024110622A1 (fr)

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CN1241595A (zh) 1999-06-30 2000-01-19 北京清大亚太科技研究中心 多重降解的组合物母粒
CN106883501A (zh) 2017-03-20 2017-06-23 兰州鑫银环橡塑制品有限公司 一种旱作农业区增强型生态降解地膜及其制备方法
CN107118398A (zh) * 2017-04-20 2017-09-01 长荣玩具（东莞）有限公司 可降解的无毒环保玩具材料及其制备方法
WO2018095905A1 (fr) * 2016-11-22 2018-05-31 Polymateria Limited Polymère dégradable et procédé de production
WO2018199494A1 (fr) 2017-04-25 2018-11-01 송경재 Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation
CN110467736A (zh) 2019-09-18 2019-11-19 枣阳市东航塑编彩印有限公司 一种可生物降解的塑料编织袋生产工艺

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Publication number Priority date Publication date Assignee Title
CN1241595A (zh) 1999-06-30 2000-01-19 北京清大亚太科技研究中心 多重降解的组合物母粒
WO2018095905A1 (fr) * 2016-11-22 2018-05-31 Polymateria Limited Polymère dégradable et procédé de production
CN106883501A (zh) 2017-03-20 2017-06-23 兰州鑫银环橡塑制品有限公司 一种旱作农业区增强型生态降解地膜及其制备方法
CN107118398A (zh) * 2017-04-20 2017-09-01 长荣玩具（东莞）有限公司 可降解的无毒环保玩具材料及其制备方法
WO2018199494A1 (fr) 2017-04-25 2018-11-01 송경재 Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation
CN110467736A (zh) 2019-09-18 2019-11-19 枣阳市东航塑编彩印有限公司 一种可生物降解的塑料编织袋生产工艺

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