EP4605241A1 - Composition based on a polyamide and a polymer comprising polyamide blocks and polyethyleneglycol blocks - Google Patents

Composition based on a polyamide and a polymer comprising polyamide blocks and polyethyleneglycol blocks

Info

Publication number
EP4605241A1
EP4605241A1 EP23793329.6A EP23793329A EP4605241A1 EP 4605241 A1 EP4605241 A1 EP 4605241A1 EP 23793329 A EP23793329 A EP 23793329A EP 4605241 A1 EP4605241 A1 EP 4605241A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
blocks
polymer
polyolefin
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23793329.6A
Other languages
German (de)
French (fr)
Inventor
Maho Yasuda
Romain David
Quentin Pineau
Claude Olivier Boissiere
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP4605241A1 publication Critical patent/EP4605241A1/en
Pending legal-status Critical Current

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2425/00—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 aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters

Definitions

  • a nonporous breathable film, or a film which is impermeable yet breathable is widely used in various applications.
  • a nonporous breathable film is advantageously used for packaging, especially for food packaging, a package of a fresh product such as a fruit, a vegetable, a freshly cut meat and fish, for example.
  • the quality and shelf life of these fresh products can be enhanced by optimizing the environment within the package enclosing them, especially by adjusting a moisture vapor transmission rate (MVTR), a permeability and a selectivity of gas such as CO2 and O2.
  • MVTR also called water vapor transmission rate (WVTR)
  • WVTR water vapor transmission rate
  • the present invention relates to a composition
  • a composition comprising:
  • the weight ratio of b/(a+b+c+d) is equal to or less than 0.5, typically between 0.05 and 0.5, preferably between 0.1 and 0.5, for example between 0.05 and 0.4.
  • the present invention makes it possible to address the need expressed above. It provides, more particularly, suitable MVTR and gas permeability, which contribute to an ideal environment in food packaging, thus to better quality and longer shelf life of packaged food products.
  • the composition according to the invention advantageously enables to provide a film with an improved quality in MVTR, gas permeability and processability.
  • the composition according to the invention is especially useful for making a film, a sheet, or a bag to be used for food packaging.
  • Such package based on the composition according to the invention may reduce withering and prevent mold growth of fresh products such as fruits and vegetables enclosed therein during the storage and/or transport.
  • a composition according to the invention comprises (a) a polyamide (PA), (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) a functionalized polyolefin, and (d) a polyolefin.
  • PA polyamide
  • PEG polyethylene glycol
  • polyamide stands for the condensation products of one or more monomers chosen from amino acids or aminocarboxylic acids, lactams and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid, more specifically,
  • amino-acids such as aminocaproic, amino-7-heptanoic, amino-11 -undecenoic and amino-12-dodecanoic acid; or one or several corresponding lactames such as caprolactame, oenanlactame and lauryllactame; or
  • the polyamide (PA) can be chosen from PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and PA12.12, preferably chosen from PA10.10, PA10.12, PA11 , PA12, PA6.12 and/or PA12.12, the first figure indicating the number of carbon atoms of the diamine and the second figure indicating the number of carbon atoms of the dicarboxylic acid; or the sole figure indicating the number of carbon atoms in the repeat unit obtained from an amino acid or lactam.
  • the polyamide (PA) is chosen from PA10.10, PA10.12, PA11 , PA12 and PA12.12.
  • the melting temperature of the polyamide (PA) of the present invention is less than 210°C, for example, less than 205°C, or less than 200°C.
  • the molecular weight of the polyamides can vary greatly, as those skilled in the art will understand.
  • mean carbon content of the repeating units means the mean of the numbers of carbon atoms of each repeating unit present in the polyamide, weighted by the molar proportion of said repeating unit relative to the total amount of polyamide blocks.
  • the mean carbon content of the repeating units of the polyamide blocks is equal to the number of carbon atoms of said repeating unit, given that a polyamide repeating unit contains, in a known manner, only one amide function.
  • the number of carbon atoms of the repeating unit is X.
  • the number of carbon atoms of the repeating unit is (X + Y)/2 since the unit X.Y comprises two amide functions.
  • the polyamide (PA) in (a) is or comprises PA11 or PA12, preferably PA11.
  • PA11 advantageously has a good miscibility with polyolefins, thus providing a good processability of the composition, that facilitates making a thinner film or sheet.
  • a polymer having polyamide blocks and polyether blocks may also be referred to as a polyether block amide (PEBA).
  • PEBA polyether block amide
  • the polymer (b) having polyamide (PA) blocks and polyethylene glycol (PEG) blocks may also be referred to as PA/PEG.
  • the polymer (b) consists of polyamide blocks and polyethylene glycol blocks.
  • Such polymers having PA blocks and PEG blocks result from the copolycondensation of polyamide sequences having reactive terminations and polyether sequences having reactive terminations, such as, among others:
  • the polyamide sequences having dicarboxylic terminations are for example obtained from condensation of aminocarboxylic alpha-omega acids, from lactames or substantially stoechiometric combinations of carboxylic diacids and diamines, in the presence of a chain limiting carboxylic diacid.
  • the polyamide blocks can be PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and PA12.12, are preferably PA10.10, PA10.12, PA11 , PA12, PA6.12, PA11.12 and/or PA12.12.
  • the polyamide blocks are PA11 or PA12, preferably PA11 .
  • the mean carbon content of the repeating units of the polyamide blocks is at least 8, preferably from 8 to 14, more preferably from 10 to 12.
  • the polyamide of the polyamide blocks in (b) is the same as the polyamide in (a).
  • the number-average molar mass Mn of the polyamide sequences PA varies between 300 and 15,000 and, preferably, from 600 to 5,000.
  • polyether blocks are included in the polymer chain having polyamide blocks and polyether blocks in the form of diols or in the form of diamines, they will be called, for the sake of simplicity, PEG blocks.
  • the numberaverage molar mass Mn of the polyether sequences is between 100 and 6,000 and is preferably between 300 and 3,000.
  • the number-average molar mass may be set by the content of chain limiter. It may be calculated according to the equation:
  • Mn 11 monomer X MWrepeating unit / II chain limiter + MWchain limiter
  • nmonomer represents the number of moles of monomer
  • Ochain limiter represents the number of moles of (e.g. diacid) limiter in excess
  • MWrepeating unit represents the molar mass of the repeating unit
  • MWchain limiter represents the molar mass of the limiter in excess.
  • the number-average molar mass of the rigid blocks and of the flexible blocks can be measured before the copolymerization of the blocks by gel permeation chromatography (GPC).
  • the polymers having PA blocks and PEG blocks can also comprise randomly- distributed moieties.
  • Such polymers can be prepared by simultaneously reacting polyether and precursors of the polyamide blocks. For example, reaction can be caused between a polyetherdiol, a lactame, (or a corresponding alpha-omega aminoacid) and a chain limiting diacid, in the presence of a small amount of water.
  • a polymer is obtained having essentially polyether blocks, polyamide blocks of greatly varying length, along with the various reagents that have reacted randomly and which are randomly distributed along the polymer chain.
  • the polymers having PA blocks and PEG blocks can be formed, in by weight, by 5 to 85% of polyether PEG blocks (and 95 to 15% PA) and, preferably from 20 to 80% polyether PEG blocks (and from 80 to 20% PA) and, more preferably, from 30 to 70% polyether PEG blocks (and 70 to 30% PA).
  • the polymer (b) comprises at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight of polyethylene glycol (PEG), with regards to the total weight of the polymer (b).
  • Such polymers having polyamide blocks and polyether blocks are available commercially from ARKEMA under the commercial name Pebax®, ®, or from EVONIK under the commercial name VESTAMID®.
  • the term "functionalized polyolefin” represents polymers of alpha-olefins and reactive units (functionalities); such reactive units are acid, anhydride or epoxy functionalities.
  • the functionalized polyolefin (c) serves as a compatibilizer or a compatibilizing agent for compatibilizing polyamides and polyolefins.
  • polyolefins previously grafted or co- or terpolymerized by unsaturated epoxides such as glycidyl (meth)acrylate, or by carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter being able to be partially or completely neutralized by metals such as Zn, etc.) or, further, by carboxylic acid anhydrides such as maleic anhydride.
  • unsaturated epoxides such as glycidyl (meth)acrylate
  • carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter being able to be partially or completely neutralized by metals such as Zn, etc.) or, further, by carboxylic acid anhydrides such as maleic anhydride.
  • co- or ter-polymerized means that the functional groups are then integrated within the main polymer chain.
  • the functionalized polyolefin (c) can be the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the grafting rate is for example from 0.01 to 5% by weight:
  • the functionalized polyolefin (c) can also be a co- or ter-polymer of at least one of the following units: (1 ) ethylene, (2) alkyl (meth)acrylate or (meth) acrylic acid or saturated carboxylic acid vinyl ester and (3) maleic anhydride or glycidyl (meth)acrylate.
  • ethylene represents preferably at least 60% by weight and where the monomer (3) represents, for example, 0.1 to 10% by weight of the copolymer:
  • the (meth)acrylic acid can be put in the form of a Zn or Li salt.
  • alkyl (meth)acrylate preferably stands for Ci to Ce alkyl methacrylates and acrylates and can be chosen from, methyl, ethyl, n-butyl, iso-butyl and 2-ethylhexyl acrylate, and most preferably methyl and ethyl methacrylate.
  • the functionalized polyolefin (c) is or comprises an ethylene/butyl acrylate/maleic anhydride copolymer or an ethylene/ethyl acrylate/glycidyl methacrylate copolymer.
  • these polyolefins can also be cross-linked using any suitable process or agent (di-epoxy, diacid, peroxy, etc.); the expression functionalized polyolefin also covers the above polyolefins crosslinked with a bi-functional reagent such as di-acid, di-anhydride, di-epoxy, etc.
  • the molecular weight, MFI index and density of these functionalized polyolefins can also vary greatly, as those skilled in the art will understand.
  • the functionalized polyolefin (c) is or comprises an ethylene and glycidyl methacrylate (GMA) copolymer.
  • GMA gives reactivity versus OH, COOH, NH2, for example, leading to optimal dispersion during melt mixing with engineering thermoplastics such as polyamide, polyesters, polyphenylene sulfide.
  • ethylene- GMA copolymer is compatible with LDPE in substantially all proportions, and with almost all other ethylene copolymers.
  • the ethylene-GMA copolymer advantageously has a good miscibility with polyolefins, thus providing a good processability, that facilitates making a thinner film or sheet.
  • the polyolefin (d) is a homopolymer or copolymer of alpha-olefins and/or diolefins, such as for example ethylene, propylene, butene-1 , octene-1 , butadiene.
  • the polyolefin (d), different from the functionalized polyolefin (c), does not contain any reactive units (functionalities) being acid, anhydride, or epoxy functionalities.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • polyethylene metallocene or polypropylene such as polyethylene, in particular LDPE (low density polyethylene), HDPE (high density polyethylene), LLDPE (linear low density polyethylene), or VLDPE (very low density polyethylene), polyethylene metallocene or polypropylene;
  • the polyolefins may have, for example, a density comprised between 0.86 and 0.965 and a melt flow index MFI comprised, for example, between 0.3 and 40 following ASTM D1238 with a standard load of 2.16 kg and at a die temperature of 190°C.
  • the polyolefins can also be cross-linked, using any suitable agent (epoxy, etc.).
  • Polyolefin mixtures are also possible.
  • the polyolefin in (d) is or comprises an ethylene-methyl acrylate copolymer or LLDPE.
  • the weight ratio of (a)/(b) is less than 1 , preferably is from 0.05 to 0.95, more preferably from 0.1 to 0.5, more preferably from 0.25 to 0.45.
  • the weight ratio of b/(a+b+c+d) is between 0.1 and 0.5.
  • (a) is present in an amount of 10-30% by weight relative to the total weight of (a)+(b)+(c)
  • (b) is present in an amount of 40-80% by weight relative to the total weight of (a)+(b)+(c)
  • (c) is present in an amount of 10-30% by weight relative to the total weight of (a)+(b)+(c).
  • (d) is present in an amount of 40-70% by weight relative to the total weight of the composition, namely relative to the total weight of
  • composition according to the invention does not comprise a styrene maleic anhydride (SMA).
  • SMA styrene maleic anhydride
  • composition according to the invention may also be mixed with further additives, such as fillers, pigments, and/or dyes.
  • (a), (b), (c) and (d) may be blended together in one step.
  • one or some of (a), (b), (c) and (d) may be blended separately in any order.
  • the method comprises a step (i) of blending (a) a polyamide, (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) a functionalized polyolefin to obtain a base polymer blend or mixture, and a step (ii) of blending (d) a polyolefin to the base polymer blend or mixture.
  • the base polymer blend or mixture is in the form of pellets before the step (ii).
  • the steps of blending may be a step of meltblending part or all of the components.
  • Melt-blending may be in particular carried out by compounding.
  • melt-blending may be carried out in an extruder or cokneader, more preferably a twin-screw extruder or a co-kneader.
  • the melt-blending may be carried out at a temperature from 140 to 300°C, preferably of from 160 to 270°C, more preferably of from 180 to 210°C.
  • the polyolefin is dry-blended to the base polymer blend or mixture.
  • the composition may be produced for example in the form of flakes, crumbs, granules or pellets. Alternatively, it may be further ground or milled to a powder. It may also be provided in the form of a paste.
  • the step (i) of blending (a), (b) and (c) to obtain a base polymer blend or mixture, and the step (ii) of blending (d) to the base mixture may be performed simultaneously or in a temporally separated manner.
  • the step (i) may be reworded as a step of obtaining a base polymer blend or mixture by blending (a), (b), and (c), and the step (ii) may be performed by blending (d) to the base polymer blend or mixture obtained by the step (i) previously, for example several hours, days, or months before the step (ii).
  • the invention also relates to a kit for obtaining the composition according to the invention.
  • the kit comprises a first component and a second component, the weight ratio of (a+b)/(c+d) being less than 1 .
  • the first component comprises (a) a polyamide (PA), (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, and
  • the second component comprises (d) a polyolefin.
  • each of (a) the polyamide, (b) the polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) the functionalized polyolefin, and (d) the polyolefin are those defined above.
  • first component and the second component may be contained, stored, or packaged in separate containers respectively, and such separate containers of two components may be optionally packaged together, by any appropriate form of packaging.
  • the containers of two components may be provided separately without any common packaging.
  • Article comprising or made from the composition and a method of making the article
  • the invention also relates to an article comprising or made from the composition according to the invention, and a method of making said article.
  • the article can be prepared using any method known in the art, for example by extrusion, injection, molding, etc.
  • the article being a film, a sheet or a bag, preferably a film, has a thickness comprised, typically, between 5 and 500 pm, preferably between 10 and 250 pm, more preferably between 20 and 100 pm, for example from 20 to 40 pm, or from 20 to 30 pm.
  • the method of making the article comprises the following steps:
  • the article obtained from the composition according to the invention, especially in form of film, give improved values of MVTR.
  • the improved values of MVTR may be between 8 and 500 g/m 2 /24h, preferably between 10 and 500 g/m 2 /24h, more preferably between 12 and 500 g/m 2 /24h, measured measured at 23°C, for a relative humidity level of 50% at a thickness of 25 pm, following the method described in ASTM standard E 96 B-Water method. Too low values of MVTR may lead to mold growth, while too high values of MVTR may lead to withering of fruits or vegetables. Such films enable an ideal environment in a package of fresh products such as fruits and vegetables. Depending on the kind of fruits or vegetable, the film can be chosen adequately according to the MVTR values.
  • the gas selectivity is defined as the ratio of the permeability of two pure gases, measured separately under the same conditions.
  • the permeability ratio of CO2 to O2 of the films obtained from the composition according to the invention is typically lower than 12 and preferably between 4 and 10, these values are valid at 0% relative humidity (0% RH) and 23°C.
  • the films obtained from the composition according to the invention give an improved processability and a higher tensile strength.
  • the tensile strength (MD) may be more than 10MPa, preferably more than 14MPa, more preferably more than 18MPa, measured according to the method described in ASTM D 638 Type IV. Such films facilitate manufacturing and processing steps.
  • the article made from the composition according to the invention is used for packaging, for example food packaging and a package for fresh products, such as fruits, vegetables, freshly cut meats and fishes.
  • the film obtained from the composition according to the invention may be only part of a package, the other part being made of any other materials.
  • the invention also relates to the use of a composition as defined above for food packaging.
  • compositions having the blend ratios outlined in Table 1 were prepared. Specifically, (a) PA, (b) PA/PEG PEBA, and (c) functionalized polyolefin were blended and compounded using a twin screw extruder into pellets. The obtained pellets were blended with (d) polyolefin, and extruded into films. For examples 12 and 13, styrene maleic anhydride (SMA) was further blended with (a) PA, (b) PA/PEG (PEBA), and (c) functionalized polyolefin and compounded into pellets, which were blended with (d) polyolefin and extruded into films.
  • SMA styrene maleic anhydride
  • Lotader® AX8840 a random copolymer of ethylene and glycidyl methacrylate (GMA) available from SK functional polymer
  • Lotader® LX4110 a random terpolymer of ethylene, acrylic ester and maleic anhydride (MAH) available from SK functional polymer
  • Lotryl® 29MA03T a random ethylene-methyl acrylate copolymer from SK functional polymer
  • Permeabilities to CO2 and O2 of the films were measured according to the method described in JIS K7126 using a gas chromatography at the temperature of 23°C and the relative humidity of 0% for a film thickness of 25 pm.
  • the results of permeabilities to CO2 and O2 are given in ml/m 2 24h atm in Table 2 below.
  • the Moisture Vapor Transmission Rate represents the amount of water vapor that passes through a film or structure over a period of 24 hours.
  • MVTR Moisture Vapor Transmission Rate
  • the films of examples 3, 4, 7-12 provided good permeability of CO2 and O2 and a relatively lower range of MVTR (from 8 to 449) compared to the films of comparative examples 1 , 2, 5 and 6. Too high values of MVTR may lead to withering of fruits or vegetables.
  • the composition according to the invention advantageously provides a film having an ideal range of MVTR which is suitable for packaging fresh products.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a composition comprising a polyamide, a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, a functionalized polyolefin, and a polyolefin, wherein the weight ratio of (a+b)/(c+d) is < 1. The invention also relates to a method of making said composition, a kit for obtaining said composition, an article comprising or made from said composition, and a method of making said article.

Description

COMPOSITION BASED ON A POLYAMIDE AND A POLYMER COMPRISING POLYAMIDE BLOCKS AND
POLYETHYLENEGLYCOL BLOCKS
TECHNICAL FIELD
The present invention relates to a composition comprising a polyamide, a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, a functionalized polyolefin, and a polyolefin. The invention also relates to a method of making said composition, a kit for obtaining said composition, an article comprising or made from said composition, and a method of making said article.
TECHNICAL BACKGROUND
A nonporous breathable film, or a film which is impermeable yet breathable is widely used in various applications. As one of such applications, a nonporous breathable film is advantageously used for packaging, especially for food packaging, a package of a fresh product such as a fruit, a vegetable, a freshly cut meat and fish, for example. The quality and shelf life of these fresh products can be enhanced by optimizing the environment within the package enclosing them, especially by adjusting a moisture vapor transmission rate (MVTR), a permeability and a selectivity of gas such as CO2 and O2. MVTR, also called water vapor transmission rate (WVTR), is the amount of water vapor that passes through a substance or material over a specific period of time. For food packaging and storage, too high values of MVTR is not desired since this may lead to withering of fruits or vegetables.
Document US 5959042 discloses a material for obtaining a nonporous breathable film comprising (a) a polyamide, (b) a polymer having PA blocks and polyether PEG blocks, (c) optionally a polyolefin, and (d) a functionalized polyolefin, in which the amounts by weight of a, b, c, and d are such that a>0, b>0, c+d>0, a+b+c+d=100, a/b>0.2, (a+b)/(c+d)>1 , and b/(a+b+c+d)<0.5.
Document EP 0476963 discloses a polymeric blend for preparing a nonporous breathable film comprising a hydrophilic block poly(ether-co-amide) containing between about 20 and about 80 weight % PEG blocks, and a hydrophobic polymer selected from any of: a) a block poly(ether-co-amide) containing essentially no PEG blocks, b) polyamide, c) a polyester, or d) a polyurethane.
However, there is still a need to optimize the MVTR, gas permeability and/or processability of films. There is more generally a need for a composition to make an improved packaging material such as a film or a sheet to preserve food or fresh products in an ideal environment. SUMMARY OF THE INVENTION
The present invention relates to a composition comprising:
(a) a polyamide (PA),
(b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks,
(c) a functionalized polyolefin, and
(d) a polyolefin, wherein the weight ratio of (a+b)/(c+d) is < 1 .
In some embodiments, the weight ratio of b/(a+b+c+d) is equal to or less than 0.5, typically between 0.05 and 0.5, preferably between 0.1 and 0.5, for example between 0.05 and 0.4.
The present invention makes it possible to address the need expressed above. It provides, more particularly, suitable MVTR and gas permeability, which contribute to an ideal environment in food packaging, thus to better quality and longer shelf life of packaged food products.
This is accomplished through a combination of a polyamide, a polymer having PA and PEG blocks, a functionalized polyolefin and a polyolefin. Notably, by selecting the weight ratio of the amount of polyamide (a) and the polymer (b) to the amount of functionalized polyolefin (c) and polyolefin (d) < 1 , the composition according to the invention advantageously enables to provide a film with an improved quality in MVTR, gas permeability and processability. As such, the composition according to the invention is especially useful for making a film, a sheet, or a bag to be used for food packaging. Such package based on the composition according to the invention may reduce withering and prevent mold growth of fresh products such as fruits and vegetables enclosed therein during the storage and/or transport.
DESCRIPTION OF EMBODIMENTS
The invention will now be described in more detail without limitation in the following description.
A composition according to the invention comprises (a) a polyamide (PA), (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) a functionalized polyolefin, and (d) a polyolefin.
(a) Polyamide
In the present application, the term "polyamide" stands for the condensation products of one or more monomers chosen from amino acids or aminocarboxylic acids, lactams and monomers resulting from the reaction between an aliphatic diamine and a dicarboxylic acid, more specifically,
- of one or several amino-acids such as aminocaproic, amino-7-heptanoic, amino-11 -undecenoic and amino-12-dodecanoic acid; or one or several corresponding lactames such as caprolactame, oenanlactame and lauryllactame; or
- of one or several substantially stoechiometric combinations of one or several aliphatic and/or cycloaliphatic and/or aromatic-aliphatic diamines, or salts thereof, with one or several aliphatic or aromatic carboxylic diacids or salts thereof; examples of such diamines are hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis(4-aminocyclohexyl)- methane (BACM), bis (3-methyl-4-amino-cyclohexyl)-methane (BMACM) and trimethylhexamethylenediamine, examples of diacids being terephthalic, isophthalic, adipic, azelaic, sebacic, suberic and docedanedicarboxylic acid; or
- any mixture of the above monomers; and
- any mixture of the resulting condensation products, optionally with other polymers compatible with the polyamides.
By way of example, the polyamide (PA) can be chosen from PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and PA12.12, preferably chosen from PA10.10, PA10.12, PA11 , PA12, PA6.12 and/or PA12.12, the first figure indicating the number of carbon atoms of the diamine and the second figure indicating the number of carbon atoms of the dicarboxylic acid; or the sole figure indicating the number of carbon atoms in the repeat unit obtained from an amino acid or lactam.
Preferably, the mean carbon content of the repeating units of the polyamide is at least 8, preferably from 8 to 14, more preferably from 10 to 12.
Typically, the polyamide (PA) is chosen from PA10.10, PA10.12, PA11 , PA12 and PA12.12.
According to one embodiment, the melting temperature of the polyamide (PA) of the present invention is less than 210°C, for example, less than 205°C, or less than 200°C.
The molecular weight of the polyamides can vary greatly, as those skilled in the art will understand.
The term “mean carbon content of the repeating units" means the mean of the numbers of carbon atoms of each repeating unit present in the polyamide, weighted by the molar proportion of said repeating unit relative to the total amount of polyamide blocks. For example, when the polyamide comprises a single repeating unit, as in the case of a PA X or of PA X.Y as defined above, the mean carbon content of the repeating units of the polyamide blocks is equal to the number of carbon atoms of said repeating unit, given that a polyamide repeating unit contains, in a known manner, only one amide function. In the case of a PA X block, the number of carbon atoms of the repeating unit is X. In the case of a PA X.Y block, the number of carbon atoms of the repeating unit is (X + Y)/2 since the unit X.Y comprises two amide functions.
Mixtures of polyamides are also possible.
Preferably, the polyamide (PA) in (a) is or comprises PA11 or PA12, preferably PA11. PA11 advantageously has a good miscibility with polyolefins, thus providing a good processability of the composition, that facilitates making a thinner film or sheet.
(b) Polymer PEBA
In the present application, a polymer having polyamide blocks and polyether blocks may also be referred to as a polyether block amide (PEBA).
The polymer (b) having polyamide (PA) blocks and polyethylene glycol (PEG) blocks may also be referred to as PA/PEG.
In some embodiments, the polymer (b) consists of polyamide blocks and polyethylene glycol blocks.
Such polymers having PA blocks and PEG blocks result from the copolycondensation of polyamide sequences having reactive terminations and polyether sequences having reactive terminations, such as, among others:
- polyamide sequences having diamine terminations with polyoxyalkylene sequences having dicarboxylic terminations;
- polyamide sequences having dicarboxylic terminations with polyoxyalkylene sequences having diamine terminations obtained by cyanoethylation and hydrogenation of aliphatic dihydroxy alpha-omega polyoxy alkylene sequences, known as polyetherdiols;
- polyamide sequences having diamine terminations with polyetherdiol sequences, the products obtained being, in this particular case, polyetheresteramides (abbreviated to PEEA below).
Such polymers are for example described in French patents Ser. Nos. 74 18913 and 77 26678 as well as in the following U.S. Pat. Nos.: 4,331 ,786, 4,115,475, 4,195,015, 4,839,441 , 4,864,014, 4,230,838 and 4,332,920 the content of which is incorporated herein by reference.
The polyamide sequences having dicarboxylic terminations are for example obtained from condensation of aminocarboxylic alpha-omega acids, from lactames or substantially stoechiometric combinations of carboxylic diacids and diamines, in the presence of a chain limiting carboxylic diacid. The polyamide blocks can be PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and PA12.12, are preferably PA10.10, PA10.12, PA11 , PA12, PA6.12, PA11.12 and/or PA12.12. Preferably, the polyamide blocks are PA11 or PA12, preferably PA11 .
Preferably, the mean carbon content of the repeating units of the polyamide blocks is at least 8, preferably from 8 to 14, more preferably from 10 to 12.
According to one embodiment, the polyamide of the polyamide blocks in (b) is the same as the polyamide in (a).
The number-average molar mass Mn of the polyamide sequences PA varies between 300 and 15,000 and, preferably, from 600 to 5,000.
Regardless of whether the polyether blocks are included in the polymer chain having polyamide blocks and polyether blocks in the form of diols or in the form of diamines, they will be called, for the sake of simplicity, PEG blocks. The numberaverage molar mass Mn of the polyether sequences is between 100 and 6,000 and is preferably between 300 and 3,000.
The number-average molar mass may be set by the content of chain limiter. It may be calculated according to the equation:
Mn = 11 monomer X MWrepeating unit / II chain limiter + MWchain limiter
In this formula, nmonomer represents the number of moles of monomer, Ochain limiter represents the number of moles of (e.g. diacid) limiter in excess, MWrepeating unit represents the molar mass of the repeating unit, and MWchain limiter represents the molar mass of the limiter in excess. The number-average molar mass of the rigid blocks and of the flexible blocks can be measured before the copolymerization of the blocks by gel permeation chromatography (GPC).
The polymers having PA blocks and PEG blocks can also comprise randomly- distributed moieties. Such polymers can be prepared by simultaneously reacting polyether and precursors of the polyamide blocks. For example, reaction can be caused between a polyetherdiol, a lactame, (or a corresponding alpha-omega aminoacid) and a chain limiting diacid, in the presence of a small amount of water. A polymer is obtained having essentially polyether blocks, polyamide blocks of greatly varying length, along with the various reagents that have reacted randomly and which are randomly distributed along the polymer chain.
The polymers having PA blocks and PEG blocks may have, for example, a Shore D hardness typically comprised between 20 and 75 and, advantageously, between 30 and 70, and an inherent viscosity comprised between 0.8 and 2.5, measured in meta-cresol at 20°C for an initial concentration of 0.5% m/m.
The polymers having PA blocks and PEG blocks can be formed, in by weight, by 5 to 85% of polyether PEG blocks (and 95 to 15% PA) and, preferably from 20 to 80% polyether PEG blocks (and from 80 to 20% PA) and, more preferably, from 30 to 70% polyether PEG blocks (and 70 to 30% PA). In some embodiments, the polymer (b) comprises at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight of polyethylene glycol (PEG), with regards to the total weight of the polymer (b).
Preferably, the polymer having PA blocks and PEG blocks comprises a single type of block. Advantageously, a polymer having PA11 blocks and PEG blocks (PA11/PEG), or a polymer having PA12 blocks and PEG blocks (PA12/PEG) is employed. PA11 advantageously has a good miscibility with polyolefins, thus providing a good processability of the composition, that facilitates making a thinner film or sheet.
One can however also employ blends of polymers having polyamide blocks and polyether blocks.
Such polymers having polyamide blocks and polyether blocks are available commercially from ARKEMA under the commercial name Pebax®, ®, or from EVONIK under the commercial name VESTAMID®.
These polymers having PA blocks and PEG blocks have characteristics of water vapor permeability and are designated as being "hydrophilic" as conventionally understood by the person skilled in the art.
(c) Functionalized polyolefin
In the present application, the term "functionalized polyolefin" represents polymers of alpha-olefins and reactive units (functionalities); such reactive units are acid, anhydride or epoxy functionalities.
The functionalized polyolefin (c) serves as a compatibilizer or a compatibilizing agent for compatibilizing polyamides and polyolefins.
As examples, we can cite the polyolefins previously grafted or co- or terpolymerized by unsaturated epoxides such as glycidyl (meth)acrylate, or by carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter being able to be partially or completely neutralized by metals such as Zn, etc.) or, further, by carboxylic acid anhydrides such as maleic anhydride. The term "co- or ter-polymerized" means that the functional groups are then integrated within the main polymer chain.
The functionalized polyolefin (c) can be the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the grafting rate is for example from 0.01 to 5% by weight:
- PE, PP, copolymers of ethylene with propylene, butene, hexene or octene containing, for example, 35 to 80% by weight ethylene;
- ethylene and vinyl acetate (EVA) copolymers containing up to 40% by weight vinyl acetate;
- ethylene and alkyl (meth)acrylate copolymers containing up to 40% by weight alkyl(meth)acrylate; - ethylene and vinyl acetate (EVA) and alkyl (meth)acrylate copolymers, containing up to 40% by weight EVA and alkyl (meth)acrylate,
- ethylene/propylene copolymers having a majority of propylene grafted with maleic anhydride and then condensed with mono-aminated polyamide (or a polyamide oligomer). These products are described in EP 0342066.
The functionalized polyolefin (c) can also be a co- or ter-polymer of at least one of the following units: (1 ) ethylene, (2) alkyl (meth)acrylate or (meth) acrylic acid or saturated carboxylic acid vinyl ester and (3) maleic anhydride or glycidyl (meth)acrylate.
As an example of functionalized polyolefins of the latter type, the following copolymers can be mentioned in which ethylene represents preferably at least 60% by weight and where the monomer (3) represents, for example, 0.1 to 10% by weight of the copolymer:
- ethylene/alkyl (meth)acrylate or (meth)acrylic acid/maleic anhydride or glycidyl methacrylate copolymers;
- ethylene/vinyl acetate/maleic anhydride or glycidyl methacrylate copolymers;
- ethylene/vinyl acetate/alkyl (meth)acrylate or (meth)acrylic acid/maleic anhydride or glycidyl methacrylate copolymers.
In the above copolymers, the (meth)acrylic acid can be put in the form of a Zn or Li salt.
The term "alkyl (meth)acrylate" preferably stands for Ci to Ce alkyl methacrylates and acrylates and can be chosen from, methyl, ethyl, n-butyl, iso-butyl and 2-ethylhexyl acrylate, and most preferably methyl and ethyl methacrylate.
Advantageously, the functionalized polyolefin (c) is or comprises an ethylene/butyl acrylate/maleic anhydride copolymer or an ethylene/ethyl acrylate/glycidyl methacrylate copolymer.
Moreover, these polyolefins can also be cross-linked using any suitable process or agent (di-epoxy, diacid, peroxy, etc.); the expression functionalized polyolefin also covers the above polyolefins crosslinked with a bi-functional reagent such as di-acid, di-anhydride, di-epoxy, etc.
The molecular weight, MFI index and density of these functionalized polyolefins can also vary greatly, as those skilled in the art will understand.
Mixtures of functionalized polyolefins are also possible.
Preferably, the functionalized polyolefin (c) is or comprises an ethylene and glycidyl methacrylate (GMA) copolymer. GMA gives reactivity versus OH, COOH, NH2, for example, leading to optimal dispersion during melt mixing with engineering thermoplastics such as polyamide, polyesters, polyphenylene sulfide. As an ethylene copolymer, ethylene- GMA copolymer is compatible with LDPE in substantially all proportions, and with almost all other ethylene copolymers. The ethylene-GMA copolymer advantageously has a good miscibility with polyolefins, thus providing a good processability, that facilitates making a thinner film or sheet.
(d) Polyolefin
The polyolefin (d) is a homopolymer or copolymer of alpha-olefins and/or diolefins, such as for example ethylene, propylene, butene-1 , octene-1 , butadiene.
The polyolefin (d), different from the functionalized polyolefin (c), does not contain any reactive units (functionalities) being acid, anhydride, or epoxy functionalities.
Examples are:
- homopolymers such as polyethylene, in particular LDPE (low density polyethylene), HDPE (high density polyethylene), LLDPE (linear low density polyethylene), or VLDPE (very low density polyethylene), polyethylene metallocene or polypropylene;
- ethylene/alpha-olefin copolymers such as ethylene/propylene;
- ethylene propylene rubbers (EPRs), styrene/ethylene-butene/butadiene (SEBS), styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene-propylene/styrene (SEPS) and ethylene/propylene/diene (EPDM) block copolymers;
- copolymers of ethylene with at least one product selected from unsaturated carboxylic acids salts or esters such as alkyl (meth)acrylate, typically methyl acrylate, or vinyl esters of saturated carboxylic acids such a vinyl acetate, in which the proportion of comonomer can be up to 40% by weight.
The copolymers mentioned above can be copolymerized in a random or sequenced manner and have a linear or branched structure.
The polyolefins may have, for example, a density comprised between 0.86 and 0.965 and a melt flow index MFI comprised, for example, between 0.3 and 40 following ASTM D1238 with a standard load of 2.16 kg and at a die temperature of 190°C. The polyolefins can also be cross-linked, using any suitable agent (epoxy, etc.).
Polyolefin mixtures are also possible.
Preferably, the polyolefin in (d) is or comprises an ethylene-methyl acrylate copolymer or LLDPE. Composition
The composition according to the invention comprises (a) the polyamide, (b) the polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) the functionalized polyolefin, and (d) the polyolefin, as defined above.
In one embodiment, in the composition according to the invention, the weight ratio of (a)/(b) is less than 1 , preferably is from 0.05 to 0.95, more preferably from 0.1 to 0.5, more preferably from 0.25 to 0.45.
Preferably, the weight ratio of b/(a+b+c+d) is between 0.1 and 0.5.
In some embodiments, (a) is present in an amount of 10-30% by weight relative to the total weight of (a)+(b)+(c), (b) is present in an amount of 40-80% by weight relative to the total weight of (a)+(b)+(c), and (c) is present in an amount of 10-30% by weight relative to the total weight of (a)+(b)+(c).
In one embodiment, (d) is present in an amount of 40-70% by weight relative to the total weight of the composition, namely relative to the total weight of
(a)+(b)+(c)+(d).
In some embodiments, (a) is present in an amount of 5-15% by weight relative to the total weight of the composition, namely the total weight of (a)+(b)+(c)+(d), (b) is present in an amount of 15-40% by weight relative to the total weight of (a)+(b)+(c)+(d), (c) is present in an amount of 5-15% by weight relative to the total weight of (a)+(b)+(c)+(d), and (d) is present in an amount of 40-70% by weight relative to the total weight of (a)+(b)+(c)+(d).
Preferably, the composition according to the invention does not comprise a styrene maleic anhydride (SMA).
The composition according to the invention may also be mixed with further additives, such as fillers, pigments, and/or dyes.
A method of making the composition
The invention also relates to a method of making the composition according to the invention.
The method comprises a step of blending:
(a) a polyamide (PA),
(b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks,
(c) a functionalized polyolefin, and
(d) a polyolefin, wherein the weight ratio of (a+b)/(c+d) is less than 1 . Each of (a) the polyamide, (b) the polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) the functionalized polyolefin, and (d) the polyolefin are those defined above.
(a), (b), (c) and (d) may be blended together in one step. Alternatively, one or some of (a), (b), (c) and (d) may be blended separately in any order.
In some embodiments, the method comprises a step (i) of blending (a) a polyamide, (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) a functionalized polyolefin to obtain a base polymer blend or mixture, and a step (ii) of blending (d) a polyolefin to the base polymer blend or mixture.
Preferably, the base polymer blend or mixture is in the form of pellets before the step (ii).
The steps of blending may be a step of dry-blending the components in a powdered form.
Alternatively and preferably, the steps of blending may be a step of meltblending part or all of the components. Melt-blending may be in particular carried out by compounding. For example, melt-blending may be carried out in an extruder or cokneader, more preferably a twin-screw extruder or a co-kneader.
The melt-blending may be carried out at a temperature from 140 to 300°C, preferably of from 160 to 270°C, more preferably of from 180 to 210°C.
Preferably, (d) the polyolefin is dry-blended to the base polymer blend or mixture.
At the end of the steps of blending, the composition may be produced for example in the form of flakes, crumbs, granules or pellets. Alternatively, it may be further ground or milled to a powder. It may also be provided in the form of a paste.
The step (i) of blending (a), (b) and (c) to obtain a base polymer blend or mixture, and the step (ii) of blending (d) to the base mixture may be performed simultaneously or in a temporally separated manner. Specifically, the step (i) may be reworded as a step of obtaining a base polymer blend or mixture by blending (a), (b), and (c), and the step (ii) may be performed by blending (d) to the base polymer blend or mixture obtained by the step (i) previously, for example several hours, days, or months before the step (ii).
Kit for obtaining the composition
The invention also relates to a kit for obtaining the composition according to the invention.
The kit comprises a first component and a second component, the weight ratio of (a+b)/(c+d) being less than 1 . The first component comprises (a) a polyamide (PA), (b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, and
(c) a functionalized polyolefin. The second component comprises (d) a polyolefin.
Each of (a) the polyamide, (b) the polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks, (c) the functionalized polyolefin, and (d) the polyolefin are those defined above.
In some embodiments, the first component and the second component may be contained, stored, or packaged in separate containers respectively, and such separate containers of two components may be optionally packaged together, by any appropriate form of packaging. Alternatively, the containers of two components may be provided separately without any common packaging.
Article comprising or made from the composition and a method of making the article
The invention also relates to an article comprising or made from the composition according to the invention, and a method of making said article.
The article can be prepared using any method known in the art, for example by extrusion, injection, molding, etc.
In some embodiments, the article is a film, a sheet, or a bag, preferably a film.
In some embodiments, the article is an article suitable for food packaging.
In some embodiments, the article, being a film, a sheet or a bag, preferably a film, has a thickness comprised, typically, between 5 and 500 pm, preferably between 10 and 250 pm, more preferably between 20 and 100 pm, for example from 20 to 40 pm, or from 20 to 30 pm.
In some embodiments, the method of making the article comprises the following steps:
- obtaining the composition by the method as defined above; and
- extruding or molding the composition into a film or a sheet.
The films obtained from the composition according to the invention are nonporous and breathable, in other words they are permeable to water vapor but impermeable to water, and, more generally, permeable to gasses but impermeable to liguids.
The article obtained from the composition according to the invention, especially in form of film, give improved values of MVTR. The improved values of MVTR may be between 8 and 500 g/m2/24h, preferably between 10 and 500 g/m2/24h, more preferably between 12 and 500 g/m2/24h, measured measured at 23°C, for a relative humidity level of 50% at a thickness of 25 pm, following the method described in ASTM standard E 96 B-Water method. Too low values of MVTR may lead to mold growth, while too high values of MVTR may lead to withering of fruits or vegetables. Such films enable an ideal environment in a package of fresh products such as fruits and vegetables. Depending on the kind of fruits or vegetable, the film can be chosen adequately according to the MVTR values.
The gas selectivity is defined as the ratio of the permeability of two pure gases, measured separately under the same conditions. The permeability ratio of CO2 to O2 of the films obtained from the composition according to the invention is typically lower than 12 and preferably between 4 and 10, these values are valid at 0% relative humidity (0% RH) and 23°C.
The films obtained from the composition according to the invention give an improved processability and a higher tensile strength. The tensile strength (MD) may be more than 10MPa, preferably more than 14MPa, more preferably more than 18MPa, measured according to the method described in ASTM D 638 Type IV. Such films facilitate manufacturing and processing steps.
These films can been prepared using any method known in the art, for example by extrusion or molding. The films have a thickness comprised, typically, between 5 and 500 pm, preferably between 10 and 250 pm, more preferably between 20 and 100 pm, for example from 20 to 40 pm, or from 20 to 30 pm. The films can be associated with other films and/or supports. For example, the film obtained from the composition according to the invention may be coextruded or laminated on a support such as a grid made of polyethylene or of PVC.
In some embodiments, the article made from the composition according to the invention is used for packaging, for example food packaging and a package for fresh products, such as fruits, vegetables, freshly cut meats and fishes. For example, the film obtained from the composition according to the invention may be only part of a package, the other part being made of any other materials.
The invention also relates to the use of a composition as defined above for food packaging.
The following examples illustrate the invention without limiting it.
EXAMPLES
The following examples illustrate the invention without limiting it.
Compositions having the blend ratios outlined in Table 1 were prepared. Specifically, (a) PA, (b) PA/PEG PEBA, and (c) functionalized polyolefin were blended and compounded using a twin screw extruder into pellets. The obtained pellets were blended with (d) polyolefin, and extruded into films. For examples 12 and 13, styrene maleic anhydride (SMA) was further blended with (a) PA, (b) PA/PEG (PEBA), and (c) functionalized polyolefin and compounded into pellets, which were blended with (d) polyolefin and extruded into films. Table 1
Unit: weight %
- Rilsan® BESNO TL: polyamide 11 (PA11) available from ARKEMA
- PEBA: PA11/PEG 1000/1500 (Mn: PA 11 blocks with molecular weight of 1000 g/mol and PEG blocks with a molecular weight of 1500 g/mol)
- Lotader® AX8840: a random copolymer of ethylene and glycidyl methacrylate (GMA) available from SK functional polymer
- Lotader® LX4110: a random terpolymer of ethylene, acrylic ester and maleic anhydride (MAH) available from SK functional polymer
- Lotryl® 29MA03T: a random ethylene-methyl acrylate copolymer from SK functional polymer
- Ultzex® 2022L: linear low density polyethylene (LLDPE) available from Prime polymer - SMA: Styrene maleic anhydride available from Polyscope Polymers B.V.
For the films of examples 1 -16 prepared as above, the measurements were performed under the following conditions:
- Machine: GTR-30XADJ4, G2700T
- Test surface: 15.2 x 10’4m2
- Detection: gas chromatography, thermal conductivity (TCD)
- Temperature: 23°C
- Relative humidity: 0%
- Carrier gas: Helium (pressure: 1 bar)
- Diffusant gases: O2, CO2 (pressure: 1 bar each)
Permeabilities to CO2 and O2 of the films were measured according to the method described in JIS K7126 using a gas chromatography at the temperature of 23°C and the relative humidity of 0% for a film thickness of 25 pm. The results of permeabilities to CO2 and O2 are given in ml/m2 24h atm in Table 2 below.
The Moisture Vapor Transmission Rate (MVTR) represents the amount of water vapor that passes through a film or structure over a period of 24 hours. For the films of 25 pm thickness prepared as above, MVTR was measured according to the method described in ASTM E 96 B-water method at 23°C, 50%RH in a Heraeus Votsch oven. The results of MVTR are given in g/m2/24h in Table 2 below.
Further, the tensile strength (MD) was measured for the films of examples prepared as above. The measurement was performed using the method described in ASTM D 638 Type IV. The results are given in MPa in Table 2 below.
Minimum thickness of a film was measured for examples prepared as above. The measurement was performed using a micrometer according to the standard ISO 4591. For the purpose of the present application, “minimum thickness” means a minimum thickness of a film which can be achieved on a continuous basis without a break in a film extrusion process.
Table 2
It can be seen from Table 2 that the films of examples 3, 4, 7-12 provided good permeability of CO2 and O2 and a relatively lower range of MVTR (from 8 to 449) compared to the films of comparative examples 1 , 2, 5 and 6. Too high values of MVTR may lead to withering of fruits or vegetables. The composition according to the invention advantageously provides a film having an ideal range of MVTR which is suitable for packaging fresh products.

Claims

1. Composition comprising:
(a) a polyamide (PA),
(b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks,
(c) a functionalized polyolefin, and
(d) a polyolefin, wherein the weight ratio of (a+b)/(c+d) is < 1 .
2. Composition according to claim 1 , wherein the weight ratio of b/(a+b+c+d) is equal to or less than 0.5, typically between 0.05 and 0.5.
3. Composition according to any one of the preceding claims, wherein the polyamide in (a) is or comprises PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and/or PA12.12, preferably PA10.10, PA10.12, PA11 , PA12, PA6.12, PA11 .12 and/or PA12.12.
4. Composition according to any one of the preceding claims, wherein the polyamide blocks in polymer (b) is or comprises PA6, PA6.6, PA6.10, PA10.10, PA10.12, PA11 , PA12, PA6.12 and/or PA12.12, preferably PA10.10, PA10.12, PA11 , PA12, PA6.12, PA11 .12 and/or PA12.12.
5. Composition according to any one of the preceding claims, wherein the mean carbon content of repeating units of the polyamide (a) and/or of the polyamide blocks in the polymer (b) is at least 8, preferably from 8 to 14, more preferably from 10 to 12.
6. Composition according to any one of the preceding claims, wherein the polyamide of the polyamide blocks in (b) is the same as the polyamide in (a).
7. Composition according to any one of the preceding claims, wherein the polymer (b) comprises at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight of polyethylene glycol (PEG), with regards to the total weight of the polymer (b). Composition according to any one of the preceding claims, wherein the functionalized polyolefin in (c) is or comprises an ethylene/butyl acrylate/maleic anhydride copolymer or an ethylene/ethyl acrylate/glycidyl methacrylate copolymer, preferably, a copolymer of ethylene and glycidyl methacrylate (GMA). Composition according to any one of the preceding claims, wherein the polyolefin in (d) is or comprises an ethylene-methyl acrylate copolymer or LLDPE. A method of making a composition, comprising a step of blending:
(a) a polyamide (PA),
(b) a polymer having polyamide (PA) blocks and polyethylene glycol (PEG) blocks,
(c) a functionalized polyolefin, and
(d) a polyolefin, wherein the weight ratio of (a+b)/(c+d) is less than 1 . Method according to claim 11 , comprising a step (i) of blending (a), (b), (c) to obtain a base polymer blend or mixture, and a step (ii) of blending (d) a polyolefin to the base polymer blend or mixture. Article, preferably an article suitable for food packing, comprising or made from the composition according to any one of claims 1 to 9, preferably the article being a film, a sheet, or a bag. Article according to claim 12, having a MVTR of between 8 and 500 g/m2/24h, preferably between 10 and 500 g/m2/24h, more preferably between 12 and 500 g/m2/24h, measured at 23°C, for a relative humidity level of 50% at a thickness of 25 pm. Method of making the article according to claim 12 or 13, comprising the following steps:
- obtaining the composition by the method according to any one of claims 10 to 11 ; and - extruding or molding the composition into a film or a sheet.
15. Use of an article according to claim 12 or 13, for food packaging.
EP23793329.6A 2022-10-18 2023-10-18 Composition based on a polyamide and a polymer comprising polyamide blocks and polyethyleneglycol blocks Pending EP4605241A1 (en)

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EP22315241.4A EP4357132A1 (en) 2022-10-18 2022-10-18 Composition based on a polyamide and a polymer comprising polyamide blocks and polyethylene glycol blocks
PCT/EP2023/078999 WO2024083915A1 (en) 2022-10-18 2023-10-18 Composition based on a polyamide and a polymer comprising polyamide blocks and polyethyleneglycol blocks

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FR2273021B1 (en) 1974-05-31 1977-03-11 Ato Chimie
FR2318185A1 (en) 1975-07-17 1977-02-11 Ato Chimie PROCESS FOR PREPARING COPOLYESTERAMIDES AS MOLDING PRODUCTS
US4195015A (en) 1976-07-30 1980-03-25 Ato Chimie Heat and aging stable copolyetheresteramides and method of manufacturing same
FR2466478B2 (en) 1979-10-02 1986-03-14 Ato Chimie PROCESS FOR THE PREPARATION OF ELASTOMERIC ALIPHATIC COPOLYETHERESTERAMIDES
FR2611727B1 (en) 1987-02-26 1989-06-16 Atochem POLYESTERAMIDES AND POLYETHERESTERAMIDES - THEIR MANUFACTURING PROCESS
FR2611726B1 (en) 1987-02-26 1989-06-16 Atochem POLYESTERAMIDES AND POLYETHERTHIOETHER-ESTER-AMIDES - THEIR MANUFACTURING PROCESS
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NZ239723A (en) 1990-09-18 1993-06-25 Chicopee Blends comprising a hydrophilic block poly (ether-co-amide) and a hydrophobic polymer
JPH05202239A (en) * 1992-01-28 1993-08-10 Toray Ind Inc Thermoplastic resin composition
EP0737709B1 (en) * 1995-04-11 2004-02-04 Atofina Packaging from polymers containing polyamide and polyether blocks for keeping freshness of products
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