WO2022268662A1 - Polymères vitrimères dérivés de polyoléfines fonctionnalisées - Google Patents

Polymères vitrimères dérivés de polyoléfines fonctionnalisées Download PDF

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WO2022268662A1
WO2022268662A1 PCT/EP2022/066599 EP2022066599W WO2022268662A1 WO 2022268662 A1 WO2022268662 A1 WO 2022268662A1 EP 2022066599 W EP2022066599 W EP 2022066599W WO 2022268662 A1 WO2022268662 A1 WO 2022268662A1
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vitrimer
functionalized polyolefin
polyolefin
polymer
functionalized
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PCT/EP2022/066599
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English (en)
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Hendrik Verhoogt
Jan Nicolaas Eddy DUCHATEAU
Theodorus Lambertus Hoeks
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Sabic Global Technologies B.V.
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Publication of WO2022268662A1 publication Critical patent/WO2022268662A1/fr

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    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • C08J2323/06—Polyethene
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention is directed to a process for preparing vitrimer polymers from functionalized polyolefins and in general to vitrimer polymers having improved melt strength and impact properties.
  • the invention is further directed to articles prepared from such vitrimer polymers.
  • thermoset resins or thermosets
  • thermoset resins have often been used to replace metals in certain applications.
  • conventional thermoset resins are subjected to specific processing requirements, which adds to processing complexities and added capital/operational expenditures.
  • thermosets are difficult to recycle due to the presence of strong crosslinking bonds, which are difficult to break down using traditional recycling techniques.
  • traditional thermoplastics are recyclable and can be formed at high temperature by injection-molding. The ability to recycle thermoplastics is a major advantage, given the increased environmental concerns on use of plastics and the drive to be more sustainable.
  • thermoplastics have certain mechanical and thermal properties that are less advantageous than that of thermoset resins. Further, in certain instances, thermoplastics suffer from processing impediments due to their narrow processing window and variable viscosities around their melting and glass transition temperature.
  • traditional thermoplastics such as polyethylenes have been modified to have “thermoset characteristics” by inducing cross-linking in the polymer network in order to improve its mechanical, thermal and chemical properties.
  • cross-linking have been induced previously by using techniques such as e-beam irradiation, or peroxides, or by using vinyl-silanes, leading to materials that cannot be recycled or reprocessed.
  • Vitrimers are a class of materials, which can be tuned to have the best of properties from both thermosets and thermoplastics.
  • vitrimers have desirable mechanical, thermal and solvent-resistant properties similar to thermoset resins while having the capacity to be reshaped and/or be repaired as that of thermoplastic materials.
  • vitrimers can be designed to be recyclable by the introduction of dynamic cross-linking bonds. The presence of dynamic cross-links in thermoplastics render such thermoplastics to be recyclable, while imparting improved mechanical and thermal properties.
  • vitrimers provide an answer to solve the above issues where vitrimers may be used as compatibilizers as well as impact modifiers.
  • vitrimers may be used as compatibilizers as well as impact modifiers.
  • vitrimers may be used as compatibilizers as well as impact modifiers.
  • vitrimers may be used as compatibilizers as well as impact modifiers.
  • vitrimers may be used as compatibilizers as well as impact modifiers.
  • vitrimers may be used as compatibilizers as well as impact modifiers.
  • it is preferred to prepare the vitrimers have high melt strength and suitable flow property. Such a properties maybe beneficial for long term polymer properties such as creep and fatigue in applications, such as pipes or foam applications while ensuring suitable processability.
  • vitrimers can render such vitrimers to be susceptible to hydrolysis and aging, affecting both product quality and performance of the vitrimer.
  • Other methods for preparing vitrimers involve the use of expensive dioxaborolane cross-linkers, with limited commercial application.
  • vitrimer materials having one or more benefits of (i) avoiding the use of catalyst during the preparation process, and (ii) producing vitrimers having improved melt strength and mechanical properties while retaining the thermoplastic characteristics of being recyclable, (iii) producing vitrimers which may be used as compatibilizers or as impact modifiers. It is yet another objective of the present invention to provide vitrimer polymers which have an excellent balance of mechanical properties, flow properties and desired melt strength characteristics.
  • the one or more objectives of the invention is achieved by a process for preparing a vitrimer polymer, comprising the steps of: a. providing a first functionalized polyolefin having polymer units derived from olefins having two to twenty carbon atoms and wherein the first functionalized polyolefin is functionalized by a first functional unit selected from carboxylic acid anhydrides, carboxylic acids, alkyl acrylates, alcohols, esters, amines, thiols and mixtures thereof; b.
  • a second functionalized polyolefin having polymer units derived from olefins having two to twenty carbon atoms and wherein the second functionalized polyolefin is functionalized by a second functional unit having a cyclic ether group; c. mixing the first functionalized polyolefin and the second functionalized polyolefin to form a precursor vitrimer mixture; and d.
  • first functionalized polyolefin or the second functionalized polyolefin preferably the first functionalized polyolefin and the second functionalized polyolefin, has a melt flow rate (MFR) of > 0.1 g/10 min and ⁇ 20.0 g/10 min, preferably > 0.1 g/10 min and ⁇ 15.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • MFR melt flow rate
  • processing of the precursor vitrimer mixture comprises any one of reactive extrusion, injection moulding, blow moulding, preferably processing of the precursor vitrimer mixture comprises reactive extrusion.
  • the precursor vitrimer mixture is processed in the presence of a promoter compound selected from water, an alcohol having one to five carbon atoms, and mixtures thereof, preferably the promoter compound is water.
  • the precursor vitrimer mixture is processed at any temperature of > 120 °C and ⁇ 300°C, preferably at any temperature > 140 °C and ⁇ 210 °C.
  • the first functional unit is present in an amount of > 0.01 wt.% and ⁇ 5.0 wt.%, preferably > 0.1 wt.% and ⁇ 2.0 wt.%, relative to the total weight of the first functionalized polyolefin; and/or the second functional unit is present in an amount of > 0.01 wt.% and ⁇ 15.0 wt.%, preferably > 0.8 wt.% and ⁇ 8.0 wt.%, relative to the total weight of the second functionalized polyolefin.
  • the ratio of molar concentration of the first functional unit to the molar concentration of the second functional unit in the precursor vitrimer mixture ranges from > 1:8 and ⁇ 8:1, preferably from > 1:4 and ⁇ 4:1, more preferably > 1:2 and ⁇ 2:1, relative to the total weight of the precursor vitrimer mixture, most preferably the ratio of molar concentration of the first functional unit to the molar concentration of the second functional unit is 2: 1.
  • the first functionalized polyolefin is selected from maleic anhydride grafted polyolefin, maleic anhydride grafted copolymers, maleic anhydride co-polymers and terpolymers, itaconic anhydride grafted polyolefin, citraconic anhydride grafted polyolefin, allylsuccinic anhydride grafted polyolefin, cyclohex-4-ene-l,2- dicarboxylic acid anhydride grafted polyolefin, 4-methyl-enecyclohex-4-ene-l,2-dicarboxylic anhydride grafted polyolefin, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride grafted polyolefin, x-methylbicyclo[2.2.1]hept-5-ene-2,2-dicarboxylic anhydride grafted polyolefin,
  • the first functionalized polyolefin is selected from maleic-anhydride grafted polyethylene (PE-MAH), maleic-anhydride grafted polypropylene, maleic-anhydride grafted copolymers of ethylene and propylene, maleic anhydride grafted copolymers of ethylene and alpha-olefins having 3 to 10 carbon atoms, maleic anhydride grafted terpolymers of propylene-ethylene and alpha-olefins having 3 to 10 carbon atoms, preferably the first functionalized polyolefin is maleic-anhydride grafted polyethylene (PE-MAH).
  • PE-MAH maleic-anhydride grafted polyethylene
  • PE-MAH maleic-anhydride grafted polypropylene
  • maleic-anhydride grafted copolymers of ethylene and propylene maleic anhydride grafted copolymers of ethylene and alpha-olefins having 3 to 10 carbon atoms
  • the second functionalized polyolefin is selected from a copolymer of olefin and glycidyl (meth)acrylate or a glycidyl (meth)acrylate grafted polyolefin, preferably the second functionalized polyolefin is a copolymer of olefin and glycidyl (meth)acrylate.
  • the second functionalized polyolefin is selected from copolymers of ethylene and glycidyl (meth)acrylate, copolymers of propylene and glycidyl (meth)acrylate, copolymers of ethylene/glycidyl (meth)acrylate and alpha-olefins having 3 to 10 carbon atoms, glycidyl (meth)acrylate grafted polyethylene, glycidyl (meth)acrylate grafted copolymers of ethylene and alpha-olefins having 3 to 10 carbon atoms, glycidyl (meth)acrylate grafted polypropylene, and mixtures thereof, preferably the second functionalized polyolefin is a copolymer of ethylene and glycidyl (meth)acrylate (PE-GMA).
  • the precursor vitrimer mixture comprises:
  • the invention is directed to a vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin, a. wherein the shear storage modulus (G’) of the vitrimer polymer > the shear loss modulus (G”) of the vitrimer polymer, when the shear storage modulus (G’) and the shear loss modulus (G”) are determined using dynamical mechanical spectroscopy (DMS) frequency sweep measurements according to ISO 6721-10 at a temperature of 190°C in a nitrogen environment using a parallel plate set-up, and at a frequency of > 0.01 rad/sec and ⁇ 100 rad/sec, at an oscillation strain of 1%; b.
  • DMS dynamical mechanical spectroscopy
  • melt flow rate > 0.1 g/10 min and ⁇ 20.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011); and c.
  • the first functionalized polyolefin is functionalized by a first functional unit selected from carboxylic acid anhydrides, carboxylic acids, alkyl acrylates, alcohols, esters, amines, thiols and mixtures thereof and the second functionalized polyolefin is functionalized by a second functional unit having a cyclic ether group.
  • the vitrimer polymer has, a.
  • oi is the complex viscosity measured at 190°C at a shear rate of 0.01 rad/sec in accordance with ISO 6721-10 and hioo is the complex viscosity measured at 190°C at a shear rate of 100 rad/sec, in accordance with ISO 6721-10.
  • the present invention is directed to vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin, wherein the vitrimer polymer is substantially free of residues derived from a vitrimer forming catalyst.
  • the vitrimer polymer is derived from a reactive extrusion reaction of a first functionalized polyolefin and a second functionalized polyolefin.
  • the present invention is directed to vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin, wherein at least one of the first functionalized polyolefin or the second functionalized polyolefin, preferably each of the first functionalized polyolefin and the second functionalized polyolefin has a melt flow rate (MFR) of > 0.1 g/10 min and ⁇ 20.0 g/10 min, preferably > 0.1 g/10 min and ⁇ 15.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • MFR melt flow rate
  • the invention is directed to an article of manufacture comprising a vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin.
  • FIG.l is a graphical representation of the complex viscosity (h) of an inventive vitrimer polymer in comparison with the complex viscosities (h) of a maleic-anhydride grafted polyethylene (PE-MAH) and a copolymer of glycidyl methacrylate and ethylene (PE-GMA) used for preparing the inventive vitrimer polymer under inventive Example I across a specific frequency range.
  • PE-MAH maleic-anhydride grafted polyethylene
  • PE-GMA copolymer of glycidyl methacrylate and ethylene
  • FIG.2 is a graphical representation of the ratio of shear storage modulus (G’) to shear loss modulus (G”) at specific frequency for each of the inventive vitrimer polymer and its constituent functionalized polyolefins under inventive Example I.
  • the invention is based, in part, on the discovery of a process for preparing vitrimer polymers from functionalized polyolefins.
  • the invention now enables a skilled artisan to prepare vitrimer polymers using a process having one or more benefits of (i) avoiding the use of a catalyst for vitrimer production and (ii) producing vitrimers having improved melt strength and mechanical properties while retaining the thermoplastic characteristics of being recyclable, (iii) producing vitrimers, which may be used as compatibilizers or as impact modifiers.
  • the invention further relates to a vitrimer polymer having improved flow property and excellent melt strength, rendering such vitrimer polymers with excellent processing characteristics and mechanical properties.
  • “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • the method of the invention can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.
  • the invention is directed to a process for preparing a vitrimer polymer, comprising the steps of: a. providing a first functionalized polyolefin having polymer units derived from olefins having two to twenty carbon atoms and wherein the first functionalized polyolefin is functionalized by a first functional unit selected from carboxylic acid anhydrides, carboxylic acids, alkyl acrylates, alcohols, esters, amines, thiols and mixtures thereof; b.
  • a second functionalized polyolefin having polymer units derived from olefins having two to twenty carbon (2-20) atoms and wherein the second functionalized polyolefin is functionalized by a second functional unit having a cyclic ether group; c. mixing the first functionalized polyolefin and the second functionalized polyolefin and forming a precursor vitrimer mixture; and d.
  • first functionalized polyolefin or the second functionalized polyolefin preferably the first functionalized polyolefin and the second functionalized polyolefin, has a melt flow rate (MFR) of > 0.1 g/10 min and ⁇ 20.0 g/10 min, preferably > 0.1 g/10 min and ⁇ 15.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • MFR melt flow rate
  • each of the first functionalized polyolefin and the second functionalized polyolefin has a melt flow rate (MFR) of ⁇ 20.0 g/10 min.
  • the invention is directed to a process for preparing a vitrimer polymer, wherein the vitrimer polymer has a ratio of shear storage modulus (G’) to shear loss modulus (G”) of >1.0, preferably > 1.0 and ⁇ 3.0, preferably > 1.0 and ⁇ 2.5, when the shear storage modulus (G’) and the shear loss modulus (G”) are determined using dynamical mechanical spectroscopy (DMS) frequency sweep measurements according to ISO 6721-10 at a temperature of 190°C in a nitrogen environment using a parallel plate set-up, and at a frequency of > 0.01 rad/sec and ⁇ 100 rad/sec, at an oscillation strain of 1%.
  • G shear storage modulus
  • G shear loss modulus
  • the expression “functionalized polyolefin” means a polyolefin, which has one or more chemical groups (functional units) attached to the main polyolefin back bone via a covalent link.
  • the expression “functionalized polyolefin” may refer to a polyolefin copolymer where an olefin monomer is copolymerized under conditions of high pressure with one or more monomer having a polar functional group.
  • the expression “mixing” as used herein means mixing of the first and second functionalized polyolefins at room temperature.
  • the mixing of the functionalized olefins may for example take place outside an extruder using hand mixing for small quantities or in a Henschel mixer for larger quantities of functionalized olefins.
  • the precursor vitrimer mixture once formed may be subsequently fed into the throat of a twin-screw extruder via a hopper.
  • the first and second functionalized polyolefins may be mixed inside an extruder, where the polyolefins are fed via two separate feeders that separately transport the functionalized polyolefins to the hopper of an extruder.
  • processing means that the precursor vitrimer polymer is subjected to a polymer processing technique suitable for obtaining the vitrimer polymer.
  • the functionalized polyolefins may for example have a suitable melt flow rate in order to impart the desired melt strength and viscosity property to the vitrimer polymer.
  • the first functionalized polyolefin and the second functionalized polyolefin has a melt flow rate (MFR) of > 0.1 g/10 min and ⁇ 20.0 g/10 min, preferably > 0.1 g/10 min and ⁇ 15.0 g/10 min, more preferably > 0.1 g/10 min and ⁇ 10.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • melt flow rate may be obtained using any suitable commercial melt flow instruments such as instruments that are made by Hanatek (UK), AML Instruments (UK), Gottfert (Germany) and the like.
  • the first functionalized polyolefin is functionalized by a first functional unit selected from carboxylic acid anhydrides, carboxylic acids, alkyl acrylates, alcohols, esters, amines, thiols and mixtures thereof.
  • the first functional unit may for example be part of a moiety chemically grafted on the polyolefin backbone chain.
  • the first functional unit may be part of a moiety copolymerized with an olefin unit.
  • the first functional unit is present in an amount of > 0.01 wt.% and ⁇ 5.0 wt.%, preferably > 0.1 wt.% and ⁇ 2.0 wt.%, relative to the total weight of the first functionalized polyolefin.
  • the first functionalized polyolefin is a maleic anhydride grafted polyolefin.
  • Non-limiting example of aliphatic groups can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • the first functionalized polyolefin is maleic-anhydride grafted polyethylene (PE- MAH).
  • the second functionalized polyolefin is functionalized by a second functional unit having a cyclic ether group.
  • the second functional unit is present in an amount of > 0.01 wt.% and ⁇ 15.0 wt.%, preferably > 0.8 wt.% and ⁇ 8.0 wt.%, relative to the total weight of the second functionalized polyolefin.
  • the second functionalized polyolefin may be diluted with a non-functionalized polyolefin so as to reduce the overall concentration of the second functional unit in the precursor vitrimer mixture.
  • the second functionalized polyolefin is a blend of a functionalized polyolefin comprising the second functional unit and a non-functionalized polyolefin.
  • the non-functionalized polyolefin is a low density polyethylene polymer (LDPE).
  • LDPE low density polyethylene polymer
  • the second functionalized polyolefin is a copolymer of olefin and glycidyl (meth)acrylate. Such a polymer can have a structure of
  • Non-limiting examples of aliphatic groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • the second functionalized polyolefin is a copolymer of ethylene and glycidyl (meth)acrylate (PE-GMA).
  • the functionalized polyolefins can be made through a high-pressure free radical process, preferably a continuous process or a reactive extrusion process.
  • suitable monomers can be polymerized under conditions to produce the functionalized polyolefins of the present invention.
  • a C2-20 olefin material(s) and a (meth)acrylate material may be contacted with a polymerization initiator at conditions suitable to produce the functionalized polyolefins.
  • the flow of the reactants can be adjusted to control the degree of polymerization.
  • Polymerization conditions that may be varied include temperature and pressures.
  • Reaction temperatures can be at least any one of, equal to one of, or between any two of 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C and 350 °C.
  • Reaction pressures can be at least any one of, equal to any one of, or between any two of 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, 300 MPa, 310 MPa, 320 MPa, 330 MPa, 340 MPa and 350 MPa.
  • Any peroxide polymer initiator can be used and examples of which are available from commercial vendors such as Arkema (France).
  • Non-limiting examples of peroxide initiators include diacyl peroxide, /-butyl peroxypivalate or the like.
  • an olefmic polymer can be reacted in the melt with a peroxide to introduce radicals in the material that will enable the reaction of an anhydride with the olefin backbone.
  • Typical temperatures used during the reactive extrusion process can be at least any one of, equal to one of, or between any two of 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C and 350 °C.
  • Any suitable commercially available peroxide polymer initiator can be used and are available from commercial vendors such as Arkema (France) or Nouryon (The Netherlands).
  • Non-limiting examples of peroxide initiators include diacyl peroxide, /-butyl peroxypivalate, or the like.
  • polyolefins such as high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), polypropylene (PP) and polyolefin elastomers (POEs) may be used to prepare the functionalized polyolefins.
  • HDPE, LLDPE, LDPE and POEs may have any suitable melt flow rate measured in accordance with ISO 1133-1 (2011).
  • the melt flow rate of the functionalized polyolefin ranges from > 5 g/10 min and ⁇ 20 g/10 min, preferably from > 5 g/10 min and ⁇ 10 g/10 min, measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • melt flow rate of the polyolefins may be suitably modified to be less than 20 g/10, measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • a functional unit e.g anhydride group, glycidyl methacrylate group
  • the process for preparing the vitrimer polymer involves blending the first functionalized polyolefin and the second functionalized polyolefin and forming a precursor vitrimer mixture.
  • the process for preparing the vitrimer polymer involves processing the precursor vitrimer mixture under conditions sufficient to react the first functionalized polyolefin and the second functionalized polyolefin and forming the vitrimer polymer.
  • the vitrimer polymer that is produced from the process of the present invention is a reaction product of the first functionalized polyolefin and the second functionalized polyolefin.
  • the precursor vitrimer mixture is processed in the presence of a promoter compound selected from water, or an aliphatic alcohol and mixtures thereof, preferably the promoter compound is water.
  • a promoter compound selected from water, or an aliphatic alcohol and mixtures thereof, preferably the promoter compound is water.
  • the aliphatic alcohol may be selected from a linear or a branched aliphatic alcohol having one to five (1-5) carbon atoms.
  • Non limiting examples of aliphatic alcohols that may be used are methanol, ethanol, propanol, t- butanol, and mixtures thereof, more preferably the aliphatic alcohol is t-butanol.
  • the promoter compound may be distinguished from a catalyst in that, the promoter compound takes part chemically during the reactive extrusion to form new covalent bonds or cleave existing covalent bonds to form the vitrimer polymer.
  • the promoter compound may induce ring opening of the maleic anhydride ring during the process of reactive extrusion leading to the formation of the vitrimer polymer product.
  • the first functionalized polyolefin is present in an amount of > 75.0 wt.% and ⁇ 85.0 wt.% relative to the total weight of the precursor vitrimer mixture and the second functionalized polyolefin is present in an amount of > 15.0 wt.% and ⁇ 25.0 wt.% relative to the total weight of the precursor vitrimer mixture.
  • precursor vitrimer mixture may in addition comprise stabilizing additives present in an amount of ⁇ 1.0 wt.%, preferably ⁇ 0.5 wt.%, relative to the total weight of the precursor vitrimer mixture.
  • stabilizing additives include anti-oxidants, UV stabilizers, nucleating agents, processing aid, masterbatch formulation and reinforcing fillers.
  • the invention is directed to a process for the preparation of a vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin wherein the first functionalized polyolefin is a polyethylene containing 0.3 wt.% grafted maleic anhydride (PE-g-0.3%-MAH) and the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • first functionalized polyolefin is a polyethylene containing 0.3 wt.% grafted maleic anhydride (PE-g-0.3%-MAH)
  • the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • each of the first functionalized polyolefin and the second functionalized polyolefin has a melt flow rate (MFR) of > 3.0 g/10 min and ⁇ 10.0 g/10 min measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • MFR melt flow rate
  • the invention is directed to a process for the preparation of a vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin wherein the first functionalized polyolefin is polyethylene containing 0.6 wt.% grafted maleic anhydride (PE-g-0.6%-MAH) and the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • first functionalized polyolefin is polyethylene containing 0.6 wt.% grafted maleic anhydride (PE-g-0.6%-MAH)
  • the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • each of the first functionalized polyolefin and second functionalized polyolefin has a melt flow rate (MFR) of > 3.0 g/10 min and ⁇ 10.0 g/10 min measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • the present invention is directed to a vitrimer polymer derived from a first functionalized polyolefin and a second functionalized polyolefin.
  • the vitrimer polymer is formed in an extruder by processing the precursor vitrimer mixture under conditions sufficient to induce reactive extrusion of the functionalized polyolefins.
  • the extruder may be operated at a temperature sufficient to induce the functionalized polyolefins to flow and promote a reaction between them.
  • the vitrimer polymer, once obtained may be quenched in a water bath and subsequently pelletized.
  • the vitrimer polymer is derived from a first functionalized polyolefin and a second functionalized polyolefin wherein the first functionalized polyolefin is polyethylene containing 0.3 wt.% grafted maleic anhydride (PE-g-0.3%-MAH) and the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • first functionalized polyolefin polyethylene containing 0.3 wt.% grafted maleic anhydride (PE-g-0.3%-MAH)
  • the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • each of the first functionalized polyolefin and second functionalized polyolefin has a melt flow rate (MFR) of > 3.0 g/10 min and ⁇ 10.0 g/10 min measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • the vitrimer polymer is derived from a first functionalized polyolefin and a second functionalized polyolefin wherein the first functionalized polyolefin is a polyethylene containing 0.6 wt.% grafted maleic anhydride (PE-g-0.6%-MAH) and the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • first functionalized polyolefin is a polyethylene containing 0.6 wt.% grafted maleic anhydride (PE-g-0.6%-MAH)
  • the second functionalized polyolefin is a copolymer containing 1.0 wt.
  • each of the first functionalized polyolefin and the second functionalized polyolefin has a melt flow rate (MFR) of > 3.0 g/10 min and ⁇ 10.0 g/10 min measured at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • MFR melt flow rate
  • DMS dynamical mechanical spectroscopy
  • the vitrimer polymer demonstrates rubber like elastic property, rendering such vitrimer polymers suitable to be used as impact modifiers in polymer blends.
  • the vitrimer polymer has a polyolefin backbone, such vitrimer polymers can be used as impact modifiers in polyolefin blends without the need to address issues related to compatibilization.
  • At least any one of the first functionalized polyolefin or the second functionalized polyolefin, preferably the first functionalized polyolefin and the second functionalized polyolefin, has a melt flow rate (MFR) > 0.1 g/10 min and ⁇ 20.0 g/10 min, as determined at 190°C at 2.16 kg load in accordance with ISO 1133-1 (2011).
  • the first functionalized polyolefin is functionalized by a first functional unit selected from carboxylic acid anhydrides, carboxylic acids, alkyl acrylates, alcohols, esters, amines, thiols and mixtures thereof and the second functionalized polyolefin is functionalized by a second functional unit having a cyclic ether group.
  • the vitrimer polymer has a complex viscosity (h) of > 1,000 Pa.s, and ⁇ 500,000 Pa.s, preferably > 1,100 Pa-s, and ⁇ 400,000 Pa-s when measured at a temperature of 190°C at any angular frequency of > 0.01 rad/s and ⁇ 100.0 rad/s, in accordance with ISO 6721-10.
  • h complex viscosity
  • the vitrimer polymer demonstrates suitable melt strength as the viscosity is high under conditions of low shear.
  • the complex viscosity of the vitrimer polymer is higher than that of the constituent functionalized polyolefins, indicating a synergistic improvement in melt strength of the inventive vitrimer polymer.
  • the high complex viscosity at low shear is particularly useful, when the vitrimer polymer in its melt state exists an extruder die and the high complex viscosity mitigates sagging of the melt.
  • the vitrimer polymer has a shear index
  • shear index (SHI) of > 100 and ⁇ 1000, preferably > 200 and ⁇ 850, preferably > 150 and ⁇ 400, wherein shear index (SHI) is defined as ho . oi/hioo where ho . oi is the complex viscosity measured at 190°C at a shear rate of 0.01 rad/sec in accordance with ISO 6721-10 and hioo is the complex viscosity measured at 190°C at a shear rate of 100 rad/sec, in accordance with ISO 6721-10.
  • the shear index (SHI) of the vitrimer polymer is higher than that of the shear index (SHI) of the constituent functionalized polyolefins from which the vitrimer polymer is prepared. Accordingly, it may be concluded that although the complex viscosity of the vitrimer polymer is high at very low shear, upon increasing the shear force, viscosity rapidly decreases at a rate faster than that of the constituent functionalized polyolefins, indicating a synergistic improvement in flow property for the vitrimer polymer. Accordingly, the inventive vitrimer polymer demonstrates specific cross-link characteristics similar to a cross-linked thermoset polymer while advantageously demonstrating flow properties similar to a thermoplastic melt.
  • the vitrimer polymer of the present invention demonstrates desired mechanical properties suitable for varied applications.
  • the vitrimer polymer has a tensile strength (stress @break) greater than the tensile strength (stress @break) of the first functionalized polyolefin and the second functionalized polyolefin, where tensile strength (stress @break) is measured in accordance with ISO 527-1.
  • the vitrimer polymer is substantially free of residues derived from vitrimer forming catalyst.
  • the vitrimer forming catalyst is present in an amount of ⁇ 1.0 wt.%, preferably ⁇ 0.05 wt.%, preferably ⁇ 0.01 wt.%, preferably 0.0 wt.%, relative to the total weight of the vitrimer polymer.
  • Typical vitrimer forming catalyst may be catalyst systems such as those described in the patent publications JP 2017202980 and US20170044361 A1.
  • the resultant vitrimer is free of any possible structural defects and contamination issues arising from the presence of trace amounts of catalyst.
  • the present invention is directed to an article of manufacture comprising the vitrimer polymer derived from the first functionalized polyolefin and the second functionalized polyolefin.
  • the vitrimers of the present invention can be used in various types of applications and articles of manufacture.
  • Non-limiting examples of the types of applications that the vitrimer polymer of the present invention can be used include motor vehicles, airplanes, boats, aeronautical construction or equipment or material, electronics, sports equipment, construction equipment and/or materials, printing, packaging, biomedical, and cosmetics.
  • Method of preparing the vitrimer polymer A specific amount (0.1786 gram) of PE-8%GMA (MFR of 5.0) was dry-blended with 7x this amount (1.2503 gram) of LDPE (MFR of 4.0) to form the second functionalized polyolefin (PE-1%-GMA) (MFR 4.3). The PE-lwt.%- GMA (second functionalized polyolefin) was then fed into a DSM Xplore Mini Compounding Unit (MCU).
  • MCU DSM Xplore Mini Compounding Unit
  • PE-g-0.3%MAH first functionalized polyolefin
  • MFR 6.0 first functionalized polyolefin
  • Rheological parameters The measurement of shear storage modulus, (G’), shear loss modulus (G”) and complex viscosity (h) was carried out using the procedure set forth under ISO 6721-10 (2015). Frequency measurements were made in the frequency range from 0.01- 100 rad/s. The measurements were made using a strain amplitude of 1 % at 190 °C.
  • Tensile testing Tensile bars (mini dog-bones; 100 x 5 x 1 mm) were obtained by directly inserting the molten polymer or vitrimer sample from the MCU into an insert that was then placed in the Xplore Injection Moulding unit to fill the mold The mould temperature was set at 60°C. The samples were tested with a Zwick Roel Z010 testing machine with a fixed crosshead speed of 50 mm/min according to the ISO 527-1 testing protocol.
  • Notched Impact Properties Impact bars were formed by directly inserting the molten polymer or vitrimer sample from the MCU into an insert that was then placed in the Xplore Injection Moulding unit to fill the mold. The notched Izod impact strength of the samples were measured at 23°C using a 5.5 J pendulum, in accordance with the standard ASTM D256.
  • Shear Modulus The shear storage modulus (G’) and shear loss modulus (G”) were determined for the PE-1%GMA, PE-g-0.3%MAH polymer and the vitrimer polymer. The details are tabul ated b el ow :
  • the high storage modulus (G 5 ) of the vitrimer polymer is indicative of a certain degree of cross-linking similar to a rubber material, which impart improved impact and melt elasticity property to the inventive vitrimer polymer.
  • the improved melt elasticity or melt strength of the vitrimer polymer is particularly advantageous for certain application where higher melt strength of the polymer is required to prevent sagging of the polymer melt and mitigate any structural defects in any products or articles that is manufactured from the vitrimer polymer.
  • the vitrimer polymer has improved flow property on increase of shearing force or frequency.
  • the vitrimer polymer has excellent melt strength making it suitable for various applications, which require materials to have high fatigue and creep resistance.
  • the complex viscosity of the vitrimer polymer is higher than that of the constituent polyolefins, which indicates high melt strength and is particularly useful for low shear polymer processing such as thermoforming or low shear extrusion process.
  • the inventive vitrimer polymer has a faster decrease in complex viscosity than that of the individual polyolefins, displaying characteristic properties of an ultra- high or a very high molecular weight thermoplastic melt, which imparts improved mechanical properties to products manufactured from the vitrimer polymer.
  • the improved mechanical properties is also evidenced from the tensile and impact measurements under Table 7, where such vitrimer polymers can be used as impact modifiers on account of their improved tensile and impact properties.
  • Example II Materials: The materials used for Example II was similar to that in Example I, except the maleic anhydride (MAH) content was double of that used in Example I (0.6 wt.% vs 0.3 wt.%). Table 8: Material details
  • Example II The vitrimer formed from Example II was subjected to mechanical testing to determine impact, tensile and shear index under testing conditions identical to that described under Example I. The results are provided as below:
  • vitrimer polymers prepared from a high melt flow rate (MFR) functionalized polyolefins.
  • MFR melt flow rate
  • vitrimer polymers were derived from a polyethylene containing 0.6 wt.% grafted maleic anhydride (PE-g-0.6%- MAH) and a copolymer containing 1.0 wt. % glycidyl methacrylate copolymerized with ethylene (PE-1%-GMA) using reactive extrusion.
  • the functionalized polyolefins, PE-g-0.6%-MAH was selected to have a melt flow rate (MFR) of 19.0 while the PE-1%-GMA was selected to have a melt flow rate (MFR) of 43.0, where the melt flow rates were measured at 190 ° C at 2.16 kg in accordance with ISO 1133-1 (2011).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un processus de préparation d'un polymère vitrimère dérivé de deux polyoléfines fonctionnalisées différentes, au moins l'une des polyoléfines fonctionnalisées constitutives, de préférence les deux polyoléfines fonctionnalisées constitutives, ayant un indice de fluidité (MFR) inférieur à 20,0 g/10 min, tel que déterminé à 190 °C à 2,16 kg de charge selon la norme ISO 1133-1 (2011). L'invention concerne en outre des polymères vitrimères ayant une propriété mécanique et une résistance à l'état fondu améliorées et des articles manufacturés préparés à partir de tels polymères vitrimères.
PCT/EP2022/066599 2021-06-25 2022-06-17 Polymères vitrimères dérivés de polyoléfines fonctionnalisées WO2022268662A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170044361A1 (en) 2014-04-24 2017-02-16 Arkema France Composition for manufacturing vitrimer resins of epoxy/anhydride type comprising a polyol
JP2017202980A (ja) 2016-05-09 2017-11-16 国立大学法人東京工業大学 動的共有結合化合物及びその組換え方法
WO2021033140A1 (fr) * 2019-08-19 2021-02-25 Sabic Global Technologies B.V. Matériaux vitrimères à base de polyoléfine contenant des unités disulfure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170044361A1 (en) 2014-04-24 2017-02-16 Arkema France Composition for manufacturing vitrimer resins of epoxy/anhydride type comprising a polyol
JP2017202980A (ja) 2016-05-09 2017-11-16 国立大学法人東京工業大学 動的共有結合化合物及びその組換え方法
WO2021033140A1 (fr) * 2019-08-19 2021-02-25 Sabic Global Technologies B.V. Matériaux vitrimères à base de polyoléfine contenant des unités disulfure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAR GOUTAM PRASANNA ET AL: "Scalable upcycling of thermoplastic polyolefins into vitrimers through transesterification", JOURNAL OF MATERIALS CHEMISTRY A, vol. 8, no. 45, 27 October 2020 (2020-10-27), GB, pages 24137 - 24147, XP055871452, ISSN: 2050-7488, DOI: 10.1039/D0TA07339C *

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