EP4508122A1 - Mousses thermoplastiques et utilisations dans des applications nécessitant une résistance et un poids léger - Google Patents

Mousses thermoplastiques et utilisations dans des applications nécessitant une résistance et un poids léger

Info

Publication number
EP4508122A1
EP4508122A1 EP23808422.2A EP23808422A EP4508122A1 EP 4508122 A1 EP4508122 A1 EP 4508122A1 EP 23808422 A EP23808422 A EP 23808422A EP 4508122 A1 EP4508122 A1 EP 4508122A1
Authority
EP
European Patent Office
Prior art keywords
foam
foams
pef
present
moieties
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
EP23808422.2A
Other languages
German (de)
English (en)
Other versions
EP4508122A4 (fr
Inventor
Hayim Abrevaya
Keith LEHUTA
Susie Martins
Aziz Sattar
Rodrigo LOBO
Erin BRODERICK
Alexey Kruglov
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.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
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 Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP4508122A1 publication Critical patent/EP4508122A1/fr
Publication of EP4508122A4 publication Critical patent/EP4508122A4/fr
Pending legal-status Critical Current

Links

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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
    • F03D1/06—Rotors
    • F03D1/065—Rotors characterised by their construction elements
    • F03D1/0675—Rotors characterised by their construction elements of the blades
    • F03D1/0679—Load carrying structures, e.g. beams
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/40—Organic materials
    • F05B2280/4007—Thermoplastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/60—Properties or characteristics given to material by treatment or manufacturing
    • F05B2280/6012—Foam
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to foamable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles made from same, including foam articles, such as panels, boards, sheets, blocks, beams and other formed articles, comprising a thermoplastic foam comprising polyethylenefuranoate (PEF) and having a surface covered by a sheet, mat, film, scrim or like surface covering, and to the uses of such articles in devices, systems and methods that require or benefit from relatively lightweight and relatively strong foam forms, and especially to environmentally advantageous and sustainable lightweight and relatively strong foam forms.
  • foam articles such as panels, boards, sheets, blocks, beams and other formed articles
  • PEF polyethylenefuranoate
  • foams are used in a wide variety of applications, it is a desirable but difficult-to-achieve goal in many applications for the foam material to be environmentally friendly while at the same time possessing excellent performance properties and being cost effective to produce.
  • Environmental considerations include not only of the recyclability and sustainability of the polymeric resin that forms the structure of the foam but also the low environmental impact of blowing agents used to form the foam, such as the Global Warming Potential (GWP) and Ozone Depletion Potential (ODP) of the blowing agent.
  • GWP Global Warming Potential
  • ODP Ozone Depletion Potential
  • thermoplastic resins including polyester resins
  • foams based on certain thermoplastic resins have been investigated for potential advantage from the perspective of being recyclable and/or sustainably sourced.
  • difficulties have been encountered in connection with the development of such materials.
  • polyester resins that are truly recyclable can be produced from sustainable sources, and which are compatible with blowing agents that are able, in combination with the thermoplastic, to produce foams with good performance properties.
  • the performance properties that are considered highly desirable include the production of high-quality closed cell foam that are low density (and therefore have a low weight in use) and at the same time having relatively high mechanical integrity and strength.
  • foam portion is made from a renewable and sustainable material that is relatively lightweight (i.e., has a density that is relatively low) and has a strength that is relatively high.
  • Such applications include, for example, use in transportation devices, such as cars, trucks, rail cars, boats, ships, aircraft and the like, since in all such applications the use of lightweight and relatively strong materials can be beneficial.
  • Other examples include sporting equipment, such as skis, snowboards, skateboards and the like, as well as stationary building structures, including for example, as roof and floor underlayment, and as components of walls, in buildings and homes.
  • Packaging applications can also benefit from foams which are provided by the present invention.
  • fluid energy transfer devices Another important example of an application which would benefit from a relatively lightweight and relatively high strength covered or faced foam made from renewable and sustainable material is in blades, foils and the like used as fluid energy transfer devices.
  • fluid energy transfer devices include the blades used on wind generators.
  • Other types of fluid energy transfer devices include vortex, tidal, oceans current oscillating hydrofoils and kites which recover air or water kinetic energy from fixed or mobile devices located in air or water.
  • a wind turbine designated generally as 2 includes a tower 4 supporting a nacelle 6 enclosing a drive train 8.
  • the wind turbine blades 10 are arranged on a hub to form a “rotor” at one end of the drive train 8 outside of the nacelle 6.
  • wind passing over the blades 10 generate lift and cause them to rotate, and the rotating blades 10 drive a gearbox 12 connected to an electrical generator 14 at the other end of the drive train 8 arranged inside the nacelle 6 along with a control system 16 that receives input from an anemometer 18.
  • a control system 16 that receives input from an anemometer 18.
  • the nacelle in many wind generators sits atop a tower that can be 120 meters off the ground for ground-based generators or and potentially even higher, and for off-shore application can be 150 meters, and potentially even higher, above the water surface for offshore generators, and for this and other reasons it is often critical to construct the various components of the wind turbine blades from materials that are relatively light in weight and at the same time sufficiently strong to withstand the forces to which the blades will be exposed. It is therefore highly important in such uses that the lightest weight material be used that can provide the necessary strength properties since this will not only improve the efficiency of operation of the wind turbine but can benefit the cost of construction and maintenance of the wind generator.
  • PET polyethylene terephthalate
  • a typical rotor blade 10 of Figure 1 is illustrated in perspective view, and Figure 3 A illustrates a cross-sectional view of the rotor blade 10 along the sectional line 3-3.
  • a typical rotor blade 10 generally includes a blade root 30 configured to be mounted or otherwise secured to the hub of the wind turbine 2 and a blade tip 32 disposed opposite the blade root 30.
  • a body shell 21 of the rotor blade is typically 1 - 6 centimeters in thickness and generally extends between the blade root 30 and the blade tip 32 along a longitudinal axis 27.
  • the body shell 21 may generally serve as the outer casing/covering of the rotor blade 10 and may define a substantially aerodynamic profile, such as by defining a symmetrical or cambered airfoilshaped cross-section. Because of the varying mechanical strength requirements along the length of the turbine blade 10, it has been common to use core materials containing polymeric foams, such as PET foam, in combination with balsa wood to form the body shell of the blade between the segment 42 and the root 30, with the balsa wood in higher concentration in regions closer to the root where strength requirements are higher.
  • core materials containing polymeric foams such as PET foam
  • the rotor blade 10 typically has a pressure side 34 and a suction side 36 extending between leading and trailing ends 26, 28 of the rotor blades 10.
  • the rotor blade 10 may also have a span 23 defining the total length between the blade root 30 and the blade tip 32 and a chord 25 defining the total length between the leading edge 26 and the trialing edge 28.
  • the chord 25 may generally vary in length with respect to the span 23, as the rotor blade 10 extends from the blade root 30 to the blade tip 32.
  • the rotor blade 10 may also include one or more longitudinally extending structural components configured to provide increased stiffness, buckling resistance and/or strength to the rotor blade 10.
  • the rotor blade 10 may include a pair of longitudinally extending shear webs 24 with spar caps 20, 22 configured to be engaged against the opposing inner surfaces 35, 37 of the pressure and suction sides 34, 36 of the rotor blades 10, respectively. Additionally, one or more shear webs 24 may be disposed between the spar caps 20, 22 so as to form a beam-like configuration.
  • the spar caps 20, 22 may generally be designed to resist bending loads and to minimize blade tip deflection and/or other loads acting on the rotor blade 10 in a generally span-wise direction (a direction parallel to the span 23 of the rotor blade 10) during operation of a wind turbine 2.
  • the spar is designed to also resist shear as well as tension and compression based on how the fibers are angled in the laminate that makes us the spar cap.
  • the spar caps 20, 22 may also be designed to withstand the span-wise compression and/or tension occurring during operation of the wind turbine 6.
  • the spar caps 20A and 22A can be integrated into a structural shell.
  • the core material is in the shell or is in the shear web or is in the spar caps of the wind turbine blade, the core is typically sandwiched between two or more face sheets that are made of a few layers glass fibers adhered with epoxy resin.
  • the facings after being rigidized, provide longitudinal stiffness and strength, whereas the core provides out-of-plane strength and stiffness.
  • the face sheets carry most of the bending and in-plane loads, while the core mostly carries the shear load.
  • thermoplastic resin With respect to the selection of thermoplastic resin, EP 3,231,836 acknowledges that while there has been interest in thermoplastic resins, in particularly polyester-based resins, this interest has encountered difficulty in development, including difficulty in identifying suitable foaming grades of such resins. Moreover, while EP 3,231,836 notes that certain polyethylene terephthalate (PET) resins, including recycled versions of PET, can be melt-extruded with a suitable physical and/or chemical blowing agent to yield closed-cell foams with the potential for low density and good mechanical properties, it is not disclosed that any such resins are at once are able to produce foams with good environmental properties and good performance properties, and are also able to be formed from sustainable sources.
  • PET polyethylene terephthalate
  • the ‘836 application identifies several possible polyester resins to be used in the formation of open-celled foams, including polyethylene terephthalate, poly butylene terephthalate, poly cyclohexane terephthalate, polyethylene naphthalate, polyethylene furanoate or a mixture of two or more of these. While the use of polyester materials to make foams that have essentially no closed cells, as required by EP ‘836, may be beneficial for some applications, a disadvantage of such structures is that in general open cell foams will exhibit relatively poor mechanical strength properties.
  • CN 108484959 discloses that making foam products based on 2,5-furan dimethyl copolyester is problematic because of an asserted problem of dissolution of foaming agent into the polyester and proposes the use of a combination of a liquid blowing agent and a gaseous blowing agent and a particular process involving sequential use of these different classes of blowing agent.
  • US 2020/0308363 and US 2020/0308396 each disclose the production of amorphous polyester copolymers that comprise starting with a recycled polyester, of which only PET is exemplified, as the main component and then proceeding through a series of processing steps to achieve an amorphous co-polymer, that is, as copolymer having no crystallinity.
  • amorphous polyester copolymers that comprise starting with a recycled polyester, of which only PET is exemplified, as the main component and then proceeding through a series of processing steps to achieve an amorphous co-polymer, that is, as copolymer having no crystallinity.
  • a wide variety of different classes of blowing agent are mentioned for use with such amorphous polymers.
  • blowing agents With respect to blowing agents, the use generally of halogenated olefin blowing agents, including hydrofluoroolefins (HFOs) and hydrochlorofluorolefins (HCFOs), is also known, as disclosed for example in US 2009/0305876, which is assigned to the assignee of the present invention, and which is incorporated herein by reference. While the '876 application discloses the use of HFO and HFCO blowing agents with various thermoplastic materials to form foams, including PET, there is no disclosure or suggestion to use any of such blowing agents with any other type of polyester resin.
  • HFOs hydrofluoroolefins
  • HCFOs hydrochlorofluorolefins
  • thermoplastic foams and in particular extruded thermoplastic foams, by using a polyester resin as disclosed herein in combination with a blowing agent comprising one of more hydrohaloolefin as disclosed herein.
  • foam articles and members including covered or faced thermoplastic foams, in which the foam is based on PEF, and preferably such PEF foams that are formed using a blowing agent comprising one of more hydrohaloolefin as disclosed herein.
  • the articles as disclosed herein overcome one or more of the deficiencies of prior art foam article, including those deficiencies describe above, and provide significant and unexpected advantages over prior art foam articles and members, as described in more detail hereinafter.
  • the present invention includes foam articles comprising: a thermoplastic, closed-cell foam and having at least a first foam surface and being any of Foams 1 - 4 as defined hereinafter; and a material different than said thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface.
  • foam articles in accordance with this paragraph are referred to herein as Foam Article 1.
  • the material of the present invention that is different than said thermoplastic, closed-cell foam and which attached to and/or integral with at least a portion of said first foam surface is sometimes referred to herein as a “facing.”
  • the present invention also includes foam articles comprising: a thermoplastic, closed-cell foam having at least a first surface; and a material different than said thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface, wherein said thermoplastic, closed-cell foam comprises thermoplastic polymer cell walls comprising at least about 0.5% by weight of ethylene furanoate moi eties and optionally one or more co-monomer moieties.
  • foam articles in accordance with this paragraph are referred to herein as Foam Article 2.
  • the present invention also includes foam articles comprising:
  • thermoplastic, closed-cell foam having at least a first foam surface wherein said thermoplastic polymer cells consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties;
  • thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface.
  • Foam Article 3A For the purposes of convenience, foam articles in accordance with this paragraph are referred to herein as Foam Article 3A.
  • the present invention also includes foam articles comprising:
  • thermoplastic, closed-cell foam having at least a first foam surface
  • thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface
  • thermoplastic polymer cells comprise cell walls comprising at least about 0.5% by weight of ethylene furanoate moieties
  • said foam has a relative foam density (RFD) of about 0.2 or less and a foam density of less than 0.3 g/cc.
  • Foam Article 3B For the purposes of convenience, foam articles in accordance with this paragraph are referred to herein as Foam Article 3B.
  • the relative foam density means the density of the foamed polymer divided by the density of the polymer before expansion, which for simplification purposes herein has been taken as 1.43 g/cc.
  • the RFD is equal to the density of the foam in g/cc divided by 1.43.
  • the present invention also includes foam articles comprising:
  • thermoplastic, closed-cell foam having at least a first, foam surface
  • thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface
  • thermoplastic polymer cells comprise cell walls comprising at least about 1% by weight of ethylene furanoate moieties
  • said foam has a relative foam density (RFD) of about 0.2 or less and a foam density of less than 0.25 g/cc; and
  • said closed thermoplastic polymer cells contain one or more blowing agents.
  • foam articles in accordance with this paragraph are referred to herein as Foam Article 3C.
  • the present invention also includes foam articles comprising:
  • thermoplastic, closed-cell foam having at least a first foam surface
  • thermoplastic, closed-cell foam attached to and/or integral with at least a portion of said first foam surface
  • thermoplastic polymer cells comprise cell walls comprising at least about 1% by weight of ethylene furanoate moieties
  • said foam has a relative foam density (RFD) of about 0.2 or less;
  • said closed thermoplastic polymer cells contain one or more FIFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms.
  • Foam Article 3D For the purposes of convenience, foam articles in accordance with this paragraph are referred to herein as Foam Article 3D.
  • the present invention also includes foam articles comprising:
  • thermoplastic, closed-cell foam having at least a first foam surface
  • thermoplastic, closed-cell foam atached to and/or integral with at least a portion of said first foam surface
  • thermoplastic polymer cells comprise cell walls comprising at least about 0.5% by weight of ethylene furanoate moieties
  • said foam has a foam density of less than 0.2 g/cc;
  • said closed thermoplastic polymer cells contain one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms.
  • Foam Article 3E For the purposes of convenience, foam articles in accordance with this paragraph are referred to herein as Foam Article 3E.
  • the present invention also provides wind turbine blades comprising a blade shell and a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3 within said blade shell .
  • Wind Turbine Blade 1 For the purposes of convenience, methods in accordance with this paragraph are referred to herein as Wind Turbine Blade 1.
  • the present invention also provides a transportation vehicle comprising a vehicle body and a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3 within said vehicle body.
  • a transportation vehicle comprising a vehicle body and a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3 within said vehicle body.
  • Vehicle 1 methods in accordance with this paragraph are referred to herein as Vehicle 1.
  • the present invention also provides stationary building structures comprising a structural component and a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3, within or otherwise attached to said vehicle body.
  • Stationary Building Structure 1 for the purposes of convenience, methods in accordance with this paragraph are referred to herein as Stationary Building Structure 1.
  • the present invention also provides sporting equipment article comprising a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3, within or otherwise attached to said sporting equipment article vehicle body.
  • a foam article of the present invention including a foam article selected from each of Foam Articles 1 - 3, within or otherwise attached to said sporting equipment article vehicle body.
  • the present invention also provides sporting equipment article comprising a foam article of the present invention, including a foam article selected from each of Foam Articles 1 - 3, within or otherwise attached to said sporting equipment article vehicle body.
  • a foam article of the present invention including a foam article selected from each of Foam Articles 1 - 3, within or otherwise attached to said sporting equipment article vehicle body.
  • Figure l is a schematic representation of an exemplary wind turbine.
  • Figure 2 is a semi-schematic representation of an exemplary wind turbine.
  • Figure 3A is cross-section of an exemplary wind turbine blade.
  • Figure 3B is cross-section of an exemplary wind turbine blade.
  • Figure 3C is cross-section of an exemplary wind turbine blade.
  • Figure 4 is a cross-section of an exemplary covered foam of the present invention in the particular form of a sandwich structure.
  • Figure 5 is a graphical representation of the strength results for the low density foams of the examples.
  • Figure 6 is a graphical representation of the strength results for the high density foams of the examples.
  • Figure 7 is a semi-schematic figure of an extruder.
  • Figures 8 and 9 are charts of the data used in Example 3 to calculate improvement in blade length and power output.
  • Transl234ze and 1234ze(E) each means transl,3,3,3-tetrafluoropropene.
  • Cisl234ze and 1234ze(Z) each means cisl,3,3,3-tetrafluoropropene.
  • 1234yf means 2,3,3,3-tetrafluoropropene.
  • 1233zd means l-chloro-3,3,3-trifluoropropene, without limitation as to isomeric form.
  • Trans1233zd and 1233zd(E) each means transl -chloro-3,3,3-trifluoropropene
  • 1224yd means cisl-chloro-2,3,3,3-tetrafluoropropane, without limitation as to isomeric form.
  • 1336mzz means 1,1,1,4,4,4-hexafluorobutene, without limitation as to isomeric form.
  • Transl336mzz and 1336mzz(E) each means trans 1,1,1,4,4,4-hexafluorobutene.
  • Cisl336mzz and 1336mzz(Z) each means cis 1,1,1,4,4,4-hexafluorobutene.
  • Closed cell foam means that a substantial volume percentage of the cells in the foam are closed, for example, about 20% by volume or more.
  • Ethylene furanoate moiety means the following structure:
  • MEG means monoethylene glycol and has the following structure:
  • FDME dimethyl 2, 5-furandi carboxylate and has the following structure:
  • PEF homopolymer means a polymer having at least 99 mole% of ethylene furanoate moi eties.
  • PEF copolymer means a polymer having at least about 0.5 mole% ethylene furanoate moieties and more than 0.5% of polymer moieties other than ethylene furanoate moieties.
  • PEF:PET copolymer means a polymer having at least about 0.5 mole% ethylene furanoate moieties and at least 0.5% of ethylene terephthalate moieties.
  • PEF means poly (ethylene furanoate) and encompasses and is intended to reflect a description of PEF homopolymer and PEF coploymer.
  • Ethylene terephthalate moiety means the structure in brackets:
  • SSP means solid-state polymerization.
  • PMDA means pyromellitic dianhydride having the following structure:
  • the present invention relates to foams and foam articles that comprise cell walls comprising PEF moieties.
  • the PEF which forms the cells walls of the foams and foam articles of the present invention can be PEF homopolymer or PEF copolymer, and particularly PEF:PET copolymer.
  • PEF homopolymer is a known material that is known to be formed by either:(a) esterification and polycondensation of FDCA with MEG; or (b) transesterification and polycondensation of FDME with MEG as illustrated below for example:
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein said polymer comprises from about 0.5 mole% to about 100 mole% of ethylene furanoate moieties and optionally at least about 1 mole% ethylene terephthalate moieties; and
  • foams in accordance with this paragraph are referred to herein as Foam 1A.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein said polymer comprises from about 0.5 mole% to about 100 mole% of ethylene furanoate moieties and optionally at least about 0.5 mole% ethylene terephthalate moieties; and
  • Foam IB foams in accordance with this paragraph are referred to herein as Foam IB.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises from about 0.5 mole% to about 20 mole% of ethylene furanoate moieties and at least about 0.5 mole% ethylene terephthalate moieties; and
  • Foam 1C foams in accordance with this paragraph are referred to herein as Foam 1C.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises from about 1 mole% to about 20 mole% of ethylene furanoate moieties and from about 80 mole% to about 99 mole% ethylene terephthalate moieties; and
  • foam ID one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms contained in the closed cells.
  • foam ID one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms contained in the closed cells.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises from about 1 mole% to about 20 mole% of ethylene furanoate moieties and from about 80 mole% to about 99 mole% ethylene terephthalate moieties; and
  • Foam IE foams in accordance with this paragraph are referred to herein as Foam IE.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises from about 0.5 mole% to about 5 mole% of ethylene furanoate moieties and from about 95 mole% to about 99.5 mole% ethylene terephthalate moieties; and
  • Foam IF foams in accordance with this paragraph are referred to herein as Foam IF.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises from about 0.5 mole% to about 2 mole% of ethylene furanoate moieties and from about 98 mole% to about 99.5 mole% ethylene terephthalate moieties; and (b) one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms contained in the closed cells.
  • Foam 1G foams in accordance with this paragraph are referred to herein as Foam 1G.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises about 1 mole% of ethylene furanoate moieties and about 99 mole% ethylene terephthalate moieties;
  • Foam 1H foams in accordance with this paragraph are referred to herein as Foam 1H.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises about 0.5 mole% of ethylene furanoate moieties and about 99.5 mole% ethylene terephthalate moieties; and
  • Foam II foams in accordance with this paragraph are referred to herein as Foam II.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises about 5 mole% of ethylene furanoate moieties and about 95 mole% ethylene terephthalate moieties;
  • foams in accordance with this paragraph are referred to herein as Foam 1J.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises about 10 mole% of ethylene furanoate moieties and about 90 mole% ethylene terephthalate moieties; and
  • Foam IK foams in accordance with this paragraph are referred to herein as Foam IK.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer has a molecular weight of at least about 10,000 kg/mole and a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein said polymer comprises about 20 mole% of ethylene furanoate moieties and about 80 mole% ethylene terephthalate moieties; and
  • Foam IL foams in accordance with this paragraph are referred to herein as Foam IL.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate wherein at least 25% of said cells are closed cells;
  • Foam 2A foams in accordance with this paragraph are referred to herein as Foam 2A.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising from about 1 mole% to about 20 mole% of ethylene furanoate moieties and about 0.5 mole% or more of ethylene terephthalate moieties; and (b) 1234ze(E) contained in the closed cells.
  • Foam 2B For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 2B.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising from about 1 mole% to about 20 mole% of ethylene furanoate moieties and about 0.5 mole% or more of ethylene terephthalate moieties;
  • Foam 2C foams in accordance with this paragraph are referred to herein as Foam 2C.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising from about 1 mole% to about 20 mole% of ethylene furanoate moieties and about 0.5 mole% or more of ethylene terephthalate moieties;
  • Foam 2D foams in accordance with this paragraph are referred to herein as Foam 2D.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising polymer comprising from about 1 mole% to about 20 mole% of ethylene furanoate moieties and about 0.5 mole% or more of ethylene terephthalate moieties;
  • Foam 2E foams in accordance with this paragraph are referred to herein as Foam 2E.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls comprising from about 1 mole% to about 20 mole% of ethylene furanoate moieties and about 0.5 mole% or more of ethylene terephthalate moieties, wherein at least 50% of said cells are closed cells;
  • a numbered foam e.g., Foam 1
  • group of numbered foams that have been defined herein
  • such reference means each of such numbered systems, including each system having a number within the group, including any suffixed numbered system.
  • reference to Foam 1 includes a separate reference to each of Foams 1A, IB, 1C, ID, etc.
  • reference to Foams 1 - 2 is understood to include a separate reference to each of Foams 1 A, IB, 1C, ID, etc., and each of foams 2A, 2B, 2C, 2D, etc.
  • this convention is used throughout the present specification for other defined materials, including Blowing Agents.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein said thermoplastic polymer: (i) comprises from about 0.5 mole% to about 99.5 mole% of ethylene furanoate moieties and optionally at least about 0.5 mole% ethylene terephthalate moieties; and (ii) has a molecular weight of at least about 25,000; and
  • Foam 3 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 3.
  • the present invention includes low-density, thermoplastic foam comprising:
  • thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein said thermoplastic polymer: (i) comprises from about 0.5 mole% to about 99.5 mole% of ethylene furanoate moieties and optionally at least about 0.5 mole% ethylene terephthalate moieties; and (ii) has a molecular weight of from about 25,000 to about 140,000; and
  • Foam 4 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 4.
  • the foams of the present invention including each of Foams 1 - 4, are formed from either PEF homopolymers, PEF copolymers, or a combination/mixture of these.
  • the foams of the present invention, including each of Foams 1 - 4 may be formed in preferred embodiments from PEF homopolymer in which the polymer has at least 99.5% by weight, or at least 99.9% of by weight, of ethylene furanoate moieties.
  • the foams of the present invention may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer, has from about 60% to about 99% by weight of ethylene furanoate moieties, or from about 70% to about 99% by weight of ethylene furanoate moieties, or from about 80% to about 99% by weight of ethylene furanoate moieties, or from about 90% to about 99% by weight of ethylene furanoate moieties or from about 95% to about 99.5% by weight of ethylene furanoate moieties.
  • the foams of the present invention may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer, has from about 40% to about 1% by weight of ethylene furanoate moieties, or from about 30% to about 1% by weight of ethylene furanoate moieties, or from about 20% to about 1% by weight of ethylene furanoate moieties, or from about 10% to about 1% by weight of ethylene furanoate moieties, or from about 5% to about 1% by weight of ethylene furanoate moieties, or from about 5% to about 0.5% by weight of ethylene furanoate moieties.
  • the foams of the present invention may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer, has from about 40% to about 1% by mole of ethylene furanoate moieties, or from about 30% to about 1% by mole of ethylene furanoate moieties, or from about 20% to about 1% by mole of ethylene furanoate moieties, or from about 10% to about 1% by mole of ethylene furanoate moieties, or from about 5% to about 1% by mole of ethylene furanoate moieties, or from about 5% to about 0.5% by mole of ethylene furanoate moieties.
  • the foams of the present invention may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer, has from about 40% to about 1% by mole of ethylene furanoate moieties and from about 60% to about 99% by mole of ethylene terephthalate moieties, or from about 30% to about 1% by mole of ethylene furanoate moieties and from about 70% to about 99% by mole of ethylene terephthalate moieties, or from about 20% to about 1% by mole of ethylene furanoate moieties and from about 80% to about 99% by mole of ethylene terephthalate moieties, or from about 10% to about 1% by mole of ethylene furanoate moieties and from about 90% to about 99% by mole of ethylene terephthalate moieties, or from about 5% to about 1% by mole of ethylene furanoate moieties and from about 9
  • the foams including each of Foams 1 - 4 are formed from PEF having the ranges of characteristics identified in Table 1 below, which are measured as described in the Examples hereof:
  • PEF including PEF homopolymer and PEF copolymer
  • PEF having these properties is achieved using one or more of the synthesis methods described above, in combination with a variety of known supplemental processing techniques, including by treatment with chain extenders, such as PMDA (and alternatives and supplements to PMDA, such as ADR, pentaerythritol (hereinafter referred to as “PENTA”) and talc as described in the present examples, and others) and/or SSP processing.
  • chain extenders such as PMDA (and alternatives and supplements to PMDA, such as ADR, pentaerythritol (hereinafter referred to as “PENTA”) and talc as described in the present examples, and others) and/or SSP processing.
  • PMDA chain extenders
  • PENTA pentaerythritol
  • talc as described in the present examples, and others
  • chain extenders generally are typically compounds that are at least di-functional with respect to reactive groups which can react with end groups or functional groups in the polyester to extend the length of the polymer chains.
  • such a treatment can advantageously increases the average molecular weight of the polyester to improve its melt strength and/or other important properties.
  • the degree of chain extension achieved is related, at least in part, to the structure and functionalities of the compounds used.
  • Various compounds are useful as chain extenders.
  • Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (hereinafter referred to as PMDA), trimellitic acid, haloformyl derivatives thereof, or compounds containing multifunctional epoxy (e.g., glycidyl), or oxazoline functional groups.
  • Nanocomposite material such as finely dispersed nanoclay may optionally be used for controlling viscosity.
  • chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema.
  • the amount of chain extender can vary depending on the type and molecular weight of the polyester components.
  • the amount of chain extender used to treat the polymer can vary widely, and in preferred embodiments ranges from about 0.1 to about 5 wt. %, or preferably from about 0.1 to about 1 .5 wt. %. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.
  • Nejib Kasmi Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achillas, and Dimitrios N. Bikiaris, which is incorporated herein by reference.
  • thermoplastic polymers which are especially advantageous for making foams, including Foams 1 - 4 and FC1 - FC11, and foam articles, including Foam Articles 1 - 4, of the present invention are identified in the following Thermoplastic Polymer Table (Table 2A), wherein all numerical values in the table are understood to be preceded by the word “about.”
  • the PEF thermoplastic polymers which are especially advantageous for making including Foams 1 - 4 and FC1 - FC11, and foam articles, including Foam Articles 1 - 4, also include those materials identified in the following Thermoplastic Polymer Table (Table 2B), wherein all numerical values in the table are understood to be preceded by the word “about.”
  • the PEF thermoplastic polymers which are especially advantageous for making including Foams 1 - 4 and FC1 - FC11, and foam articles, including Foam Articles 1 - 4, of the present invention also include those materials identified in the following Thermoplastic Polymer Table (Table 2C), wherein all numerical values in the table are understood to be preceded by the word “about.”
  • Table 2C Thermoplastic Polymer Table
  • thermoplastic polymers identified in the first column in each of rows in the TPP table above and reference to each of these numbers is a reference to a thermoplastic polymer as defined in the corresponding columns of that row.
  • Reference to a group of TPPs that have been defined in the table above by reference to a TPP number means separately and individually each such numbered TPP, including each TPP having the indicated number, including any such number that has a suffix. So for example, reference to TPP1 is a separate and independent reference to TPP1 A, TPP IB, TPP1C, TPP ID and TPP IE.
  • TPP1 - TPP2 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D, TTP1E, TPP2A, TPP2B, TPP2C, TPP2D and TPP IE. This use convention is used for the Foamable Composition Table and the Foam Table below as well.
  • the present invention includes, but is not limited to, applicant’s discovery that a select group of blowing agents are capable of providing foamable PEF foamable compositions and PEF foams and foam articles, including Foam Articles 1 - 4, having a difficult-to-achieve and surprising combination of physical properties, including low density as well as good mechanical strength properties.
  • the blowing agent used in accordance with the present invention preferably comprises one or more hydrohaloolefins having three or four carbon atoms.
  • a blowing agent in accordance with this paragraph is sometimes referred to herein as Blowing Agent 1A.
  • blowing agent used in accordance with the present invention preferably consists essentially of one or more hydrohaloolefins having three or four carbon atoms.
  • Blowing Agent IB a blowing agent in accordance with this paragraph is sometimes referred to herein as Blowing Agent IB.
  • blowing agent used in accordance with the present invention preferably conisits essentially of one or more hydrohaloolefins having three or four carbon atoms.
  • Blowing Agent 1C a blowing agent in accordance with this paragraph is sometimes referred to herein as Blowing Agent 1C.
  • the blowing agent used in accordance with of the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (referred to hereinafter for convenience as Blowing Agent 2A); or comprises one or more of trans 1234ze, 1336mzz, trans 1233 zd and ci si 224yd (referred to hereinafter for convenience as Blowing Agent 3A) ; or comprises one or more of transl234ze, transl336mzz, transl233zd and cisl224yd (referred to hereinafter for convenience as Blowing Agent 4A); or comprises one or more of transl234ze and transl336mzz (referred to hereinafter for convenience as Blowing Agent 5A); or comprises transl234ze (referred to hereinafter for convenience as Blowing Agent 6A) ; or comprises transl336mzz (referred to hereinafter for convenience as Blowing Agent 7A); or comprises cisl336mzz (referred to hereinafter for convenience as Blo
  • the blowing agent used in accordance with of the present invention preferably consists essentially of one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (referred to hereinafter for convenience as Blowing Agent 2B); or consists essentially of one or more of transl234ze, 1336mzz, transl233zd and cisl224yd (referred to hereinafter for convenience as Blowing Agent 3B) ; or consists essentially of one or more of trans 1234ze, transl336mzz, trans 1233 zd and ci si 224yd (referred to hereinafter for convenience as Blowing Agent 4B); or consists essentially of one or more of transl234ze and transl336mzz (referred to hereinafter for convenience as Blowing Agent 5B); or consists essentially of transl234ze (referred to hereinafter for convenience as Blowing Agent 6B) ; or consists essentially of transl336mzz (referred to hereinafter for convenience as Blowing
  • the blowing agent used in accordance with of the present invention preferably consists of one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (referred to hereinafter for convenience as Blowing Agent 2B); or consists of one or more of trans 1234ze, 1336mzz, trans 1233 zd and ci si 224yd (referred to hereinafter for convenience as Blowing Agent 3B) ; or consists of one or more of transl234ze, transl336mzz, transl233zd and cisl224yd (referred to hereinafter for convenience as Blowing Agent 4B); or consists of one or more of transl234ze and transl336mzz (referred to hereinafter for convenience as Blowing Agent 5B); or consists of transl234ze (referred to hereinafter for convenience as Blowing Agent 6B) ; or consists of transl336mzz (referred to hereinafter for convenience as Blowing Agent 7B); or consists of cisl
  • blowing agent of the present invention including each of Blowing Agents 1 - 11, can include, in addition to each of the above-identified blowing agent(s), co-blowing agent including in one or more of the optional potential coblowing agents as described below.
  • the present foamable compositions, foams, and foaming methods include a blowing agent as described according described herein, wherein the indicated blowing agent (including the compound or group of compound(s) specifically identified in each of Blowing Agent 1 - 11) is present in an amount, based upon the total weight of all blowing agent present, of at least about 50% by weight, or preferably at least about 60% by weight, preferably at least about 70% by weight, or preferably at least about 80% by weight, or preferably at least about 90% by weight, or preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total of all blowing agent components.
  • the indicated blowing agent including the compound or group of compound(s) specifically identified in each of Blowing Agent 1 - 11
  • the indicated blowing agent is present in an amount, based upon the total weight of all blowing agent present, of at least about 50% by weight, or preferably at least about 60% by weight, preferably at least about 70% by weight, or preferably at least about 80% by weight, or
  • blowing agent of the present invention can include one or more co-blowing agents which are not included in the indicated selection, provided that such co-blowing agent in the amount used does not interfere with or negate the ability to achieve relatively low- density foams as described herein, including each of Foams 1 - 4, and preferably further does not interfere with or negate the ability to achieve foam with mechanical strengths properties as described herein.
  • HFCs saturated hydrocarbons or hydrofluorocarbons
  • HFC co-blowing agents include, but are not limited to, one or a combination of difluoromethane (HFC-32), fluoroethane (HFC- 161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC- 236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all isomers of all such HFCs.
  • HFC-32 difluoromethane
  • HFC- 161 fluoroethane
  • HFC-152 difluoroethane
  • HFC-143 trifluoroethane
  • HFC-134
  • the present blowing agent compositions also may include in certain preferred embodiments, for example, iso, normal and/or cyclopentane and butane and/or isobutane.
  • Other materials such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such as dichloroethylene (preferably trans-di chloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as, for example, ethanol and/or propanol and/or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxy methane and diethoxy methane)), and methyl formate, organic acids (such as
  • the foams of the present invention including each of Foams 1 - 4, or foam made from PEF polymer of the present invention, including Thermoplastic Polymer TPP1A - TPP22E, or any of the foams described in Examples 1 - 22, may generally be formed from a foamable composition of the present invention.
  • the foamable compositions of the present invention may be formed by combining a PEF polymer of the present invention, including each of Thermoplastic Polymer TPP1A - TPP22E, with a blowing agent of the present invention, including each of Blowing Agents 1 - 11.
  • Foamable compositions that are included within the present invention and which provide particular advantage in connection with forming the foams of the present invention, are described in the following Foamable Composition Table (Table 3 A and Table 3B), in which all numerical values in the table are understood to be preceded by the word “about” and in which the following terms used in the table have the following meanings:
  • CBAG1 means co-blowing agent selected from the group consisting of 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf and combinations of two or more of these.
  • CBAG2 means co-blowing agent selected from the group consisting of water, CO2, Cl - C6 hydrocarbons (HCs) HCFCs, Cl - C5 HFCs, C2 - C4 hydrohaloolefins, C1-C5 alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers, Cl - C4 esters, organic acids and combinations of two or more of these.
  • HCs hydrocarbons
  • Cl - C5 HFCs Cl - C5 HFCs
  • C2 - C4 hydrohaloolefins C1-C5 alcohols
  • C1-C4 aldehydes C1-C4 ketones
  • C1-C4 ethers C1-C4 ethers
  • Cl - C4 esters organic acids and combinations of two or more of these.
  • CCBAG3 means co-blowing agent selected from the group consisting of water, CO2, isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-dichloroethylene, ethanol, propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxy methane, diethoxy methane, methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1 -difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1 , 1 , 1 ,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC
  • any one or more of a variety of known techniques for forming a thermoplastic foam can be used in view of the disclosures contained herein to form a foam of the present invention, including each of Foams 1 - 4, all such techniques and all foams and foamed articles, including Foamed Articles 1 - 3 formed thereby are within the broad scope of the present invention.
  • definition of the foams in the Table below all begin with only the letter F, in contrast to the foams defined by the paragraphs in the summary above, which begin with the capitalized phrase Foamable Composition.
  • the forming step involves first introducing into a PEF polymer of the present invention, including each of TPP1 - TPP22, a blowing agent of the present invention, including each of Blowing Agents 1 - 31, to form a foamable PEF composition comprising PEF and blowing agent.
  • a preferred method for forming a foamable PEF composition of the present invention is to plasticize the PEF, preferably comprising heating the PEF to its melt temperature, preferably above its melt temperature, and thereafter exposing the PEF melt to the blowing agent under conditions effective to incorporate (preferably by solubilizing) the desired amount of blowing agent into the polymer melt.
  • the foaming methods of the present invention comprise providing a foamable composition of the present invention, including each of FC1 - FC13 and foaming the provided foamable composition.
  • the foaming methods of the present invention comprising providing a foamable composition of the present invention, including each of FC1 - FC13, and extruding the provided foamable composition to form a foam of the present invention and then forming a foam article of the present invention, including each of Foam Articles 1 - 4.
  • Foaming processes of the present invention can include batch, semi-batch, continuous processes, and combinations of two or more of these.
  • Batch processes generally involve preparation of at least one portion of the foamable polymer composition, including each of FC1 - FC13, in a storable state and then using that portion of foamable polymer composition at some future point in time to prepare a foam.
  • Semi-batch process involves preparing at least a portion of a foamable polymer composition, including each of FC1 - FC13, and intermittently expanding that foamable polymer composition into a foam including each of Foams 1 - 4 and each of foams Fl - F8, all in a single process.
  • thermoplastic foams via an accumulating extrusion process.
  • the present invention thus includes processes that comprises: 1) mixing PEF thermoplastic polymer, including each of TPP1 - TPP22, and a blowing agent of the present invention, including each of Blowing Agents 1 - 31, under conditions to form a foamable PEF composition; 2) extruding the foamable PEF composition, including each of FC1 - FC13, into a holding zone maintained at a temperature and pressure which does not allow the foamable composition to foam, where the holding zone preferably comprises a die defining an orifice opening into a zone of lower pressure at which the foamable polymer composition, including each of FC1 - FC13, foams and an openable gate closing the die orifice; 3) periodically opening the gate while substantially concurrently applying mechanical pressure by means of a movable ram on the foamable polymer composition, including each of FC1 - FC 13, to eject it from the holding zone through the die orifice into
  • the present invention also can use continuous processes for forming the foam.
  • a continuous process involves forming a foamable PEF composition, including each of FC1 - FC13, and then expanding that foamable PEF composition without substantial interruption.
  • a foamable PEF composition, including each of FC1 - FC13 may be prepared in an extruder by heating the selected PEF polymer resin, including each of TPP 1 - TPP22, to form a PEF melt, incorporating into the PEF melt a blowing agent of the present invention, including each of Blowing Agents 1 - 11, preferably by solubilizing the blowing agent into the PEF melt, at an initial pressure to form a foamable PEF composition comprising a substantially homogeneous combination of PEF and blowing agent, including each of FC1 - FC13, and then extruding that foamable PEF composition through a die into a zone at a selected foaming pressure and allowing the foamable PEF composition to expand into a foam, including each of Foams 1 - 4
  • the foamable PEF composition which comprises the PEF polymer, including each of FC1 - FC13, and the incorporated blowing agent, including each of Blowing Agents 1 - 11, may be cooled prior to extruding the composition through the die to enhance certain desired properties of the resulting foam, including each of Foams 1 - 6 and each of foams Fl - F8.
  • the methods can be carried out, by way of example, using extrusion equipment of the general type disclosed in Figure 8.
  • the extrusion apparatus can include a raw material feed hopper 10 for holding the PEF polymer 15 of the present invention, including each of TPP1 - TPP22, and one or more optional components (which may be added with the PEF in the hopper or optionally elsewhere in the process depending on the particular needs of the user).
  • the feed materials 15, excluding the blowing agent, can be charged to the hopper and delivered to the screw extruder 10.
  • the extruder 20 can include thermocouples (not shown) located at three points along the length thereof and a pressure sensor (not shown) at the discharge end 20A of the extruder.
  • a mixer section 30 can be located at the discharge end 20A of the extruder for receiving blowing agent components of the present invention, including each of Blowing Agents 1 - 31, via one or more metering pumps 40A and 40B and mixing those blowing agents into the PEF melt in the mixer section. Sensors (not shown) can be included for monitoring the temperature and pressure of the mixer section 30.
  • the mixer section 30 can then discharge the foamable composition melt of the present invention, including each of FC1 - FC13, into a pair of melt coolers 50 oriented in series, with temperature sensors (not shown) located in each cooler to monitor the melt temperature.
  • the melt is then extruded through a die 60, which also had temperature and pressure sensors (not shown) for monitoring the pressure and temperature at the die.
  • the die pressure and temperature can be varied, according to the needs of each particular extrusion application to produce a foam 70 of the present invention, including each of including each of Foams 1 - 4 and each of foams Fl - F8 described below.
  • the foam can then be carried away from the extrusion equipment by a conveyor belt 80.
  • the foamable polymer compositions of the present invention may optionally contain additional additives such as nucleating agents, cellcontrolling agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents and thermally insulating additives.
  • Nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such azodi carbonamide or sodium bicarbonate and citric acid.
  • IR attenuating agents and thermally insulating additives can include carbon black, graphite, silicon dioxide, metal flake or powder, among others.
  • Flame retardants can include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
  • brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
  • additional optional additives can be introduced into the foam at various times and that various locations in the process according to known techniques, and all such additives and methods of addition or within the broad scope of the present invention.
  • the foams of the present invention are formed in a commercial extrusion apparatus and have the properties as indicated in the following Table 4, with the values being measured as described in the Examples hereof: TABLE 4
  • the foams of the present invention have wide utility.
  • the present foams, including each of Foams 1 - 4 and foams Fl - F8, have unexpected advantage in applications requiring low density and/or good compression and/or tensile and/or shear properties, and/or longterm stability, and/or sustainable sourcing, and/or being made from recycled material and being recyclable.
  • the present foams including each of Foams 1 - 6 and each of foams Fl - F8, have unexpected advantage in: wind energy applications (wind turbine blades (shear webs, shells, cores, and root); marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors); industrial low weight applications; automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft).
  • wind energy applications wind turbine blades (shear webs, shells, cores, and root)
  • marine applications hulls, decks, superstructures, bulkheads, stringers, and interiors
  • industrial low weight applications automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft).
  • PEF:PET copolymers can be formed by any means to those known to those skilled in the art, including but not limited to those procedures described in the Examples hereof.
  • the foams of the present invention including each of Foam 1 - 4, are formed from either PEF homopolymers, PEF copolymers, PEF:PET copolymers or a combination/mixture of these.
  • the foams including each of Foam 1 - 4, may be formed in preferred embodiments from PEF homopolymer in which the polymer has at least 99.5% by weight, or at least 99.9% of by weight, of ethylene furanoate moieties.
  • the foams of the present invention may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer that has from about 0.5% to about 99% by weight of ethylene furanoate moieties.
  • the invention includes foams, including each of Foam 1 - 3, wherein the thermoplastic polymer consists essentially of the components as described in the following table:
  • the foams of the present invention can comprise closed cell walls comprising each of the thermoplastic polymers of the present invention, including each of TMP1 - TMP12 describe in the table above.
  • thermoplastic polymers of the present invention including each of TMP1 - TMP12 describe in the table above.
  • PEF copolymers it is contemplated that those skilled in the art will be able, in view of the teachings contained herein, to select the type in an amount of co-polymeric materials to be used within each of the ranges described herein to achieve the desired enhancement/modification of the polymer without undue experimentation.
  • the TMPs of the present invention may be formed with a variety of physical properties, including the following ranges of polymer characteristics, which are measured as described in the Examples hereof:
  • PEF polymer according to the present invention including PEF:PET copolymers of the present invention
  • having these properties is achieved using one or more of the synthesis methods described above, in combination with a variety of known supplemental processing techniques, including by treatment with chain extenders, such as PMDA, and/or SSP processing.
  • chain extenders generally are typically compounds that are at least di-functional with respect to reactive groups which can react with end groups or functional groups in the polyester to extend the length of the polymer chains.
  • such a treatment can advantageously increase the average molecular weight of the polyester to improve its melt strength and/or other important properties.
  • the degree of chain extension achieved is related, at least in part, to the structure and functionalities of the compounds used.
  • Various compounds are useful as chain extenders.
  • Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, haloformyl derivatives thereof, or compounds containing multi-functional epoxy (e.g., glycidyl), or oxazoline functional groups.
  • Nanocomposite material such as finely dispersed nanoclay may optionally be used for controlling viscosity.
  • Commercial chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema.
  • the amount of chain extender can vary depending on the type and molecular weight of the polyester components.
  • the amount of chain extender used to treat the polymer can vary widely, and in preferred embodiments ranges from about 0.1 to about 5 wt. %, or preferably from about 0.1 to about 1.5 wt. %. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.
  • An example of the process for SSP processing of polyethylene furanoate) is provided in the article “Solid-State Polymerization of Poly (ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase,” Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achillas, and Dimitrios N. Bikiaris, which is incorporated herein by reference.
  • the present invention involves applicant’s discovery that a select group of blowing agents are capable of providing foamable PEF compositions, including each of Foamable Composition 1, and PEF foams, including Foams 1 - 3, having a difficult to achieve a surprising combination of physical properties, including low density as well as good mechanical strengths properties.
  • the foams of the present invention are thermoplastic foams, and generally it is contemplated that any one or more of a variety of known techniques for forming a thermoplastic foam can be used in view of the disclosures contained herein, and all such techniques and all foams formed thereby or within the broad scope of the present invention.
  • the foams and foam articles of the present invention have wide utility.
  • the present foam articles, including each of Foam Articles 1 - 3, have unexpected advantage, especially in applications requiring low density and/or good compression and/or tensile and/or shear properties, and/or long-term stability, and/or sustainable sourcing, and/or being made from recycled material and being recyclable.
  • the present foam articles including each of Foam Articles 1 - 3, have unexpected advantage in: wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles); marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors); industrial low weight applications; automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft); stationary building structure; and sporting equipment.
  • wind energy applications wind turbine blades (shear webs, shells, cores, and nacelles); marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors); industrial low weight applications; automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft); stationary building structure; and sporting equipment.
  • the foam articles of the present invention including each of Foam Articles 1 - 3, generally comprise a foam which has a facing on at least a portion of the surface thereof.
  • reference to a numbered foam article or group of numbered foam articles that have been defined herein means each of such numbered foam articles, including each foam article having a number within the group, including any suffixed number.
  • reference to Foam Article 3 includes reference to each of Foam Articles 3A, 3B, 3C and 3D.
  • the size and shape of the foam used in the present foam articles can vary widely within the scope of the present invention depending on the use that will be made of the article, and all such sizes and shapes are within the scope of the present invention.
  • the foam article will be in the form of a three dimensional form in which the length and/or width are much larger in dimension than the thickness Tn other applications, the form of the article can be characterized as a block, slab, panel or the like, or as a particular shape such as I-beam, U-shaped or other specific shape.
  • Figure 4 illustrates a form in which the foam article is in the general shape of a sheet or panel that has a facing on each side of the sheet or panel.
  • a foam article according to the present invention comprises a core 1 of PEF foam of the present invention, including each of TMP 1 - 12 as defined below, and at least one reinforcing facing 2 and at least one connecting and/or integrating layer 3.
  • the connecting/integrating layer may comprise a layer of adhesive, for example, or may be formed by integrating the core material and the facing material without the use of a separate adhesive, such as would occur, for example, by melting the surfaces of the two materials together to form a connecting/integrating region.
  • the facing can be any material appropriate to the intended use, as mentioned above, but in many applications the facing 2 is a sheet or film of fibrous material as described above.
  • the fibers of a preferred facing 2 may be, for example, in the form of a woven or nonwoven mat (or a mat comprising a combination of woven and nonwoven fibers), including crimped mats that can be either woven or non-woven, and the fibers can be oriented or non-oriented (i.e., random).
  • the orientation can include unidirectional, bi-directional, biaxial, tri-axial, quad-axial and combinations of any of these.
  • the connecting/integrating film, layer or region 3 can be any material and in any thickness needed to attach or integrate the facing 3 to the core 1. Furthermore, while the film or layer 3 is shown as generally as being between the facing 2 and the core 1, it will be understood and appreciated by those skilled in the art that the connecting layer or film generally extends into each of the foam core 1 and the facing 2. In certain preferred embodiments, the film or layer 3 can comprise adhesive material, such as an epoxy adhesive, which bonds the core 1 and the facing sheet 2 together.
  • the processing of forming the foam articles of the present invention involves steps which provide a strong chemical and/or physical bond between facing 2 and the foam 1 , and all such steps are within the scope of the present invention.
  • the facing 2 comprises a plurality of inter-bonded sheets or mats which can be the same or different and are bound to one another by appropriate means, including inter-bonding layers of adhesive or resin or inter-bonding regions formed by material integration (e.g., melting together to form an integrated region).
  • material integration e.g., melting together to form an integrated region.
  • the number of inter-bonded sheets that make-up the facing 2 can vary widely, and in preferred embodiments the facing comprises from 2 to 10 inter-bonded sheets, and even more preferably from about 3 to about 5 inter-bonded sheets.
  • the face sheet can vary from about 0.1 mm to about 3 mm, or from about 0.4 mm to about 1.5 mm.
  • the relative thickness of the foam compared to the face sheet can vary over a wide range depending on the particular application, and that those skilled in the art will be able to make appropriate selections in view of the teachings contained herein, and that in general the face sheet thickness will be less than the thickness of the foam.
  • the foam articles of the present invention include a facing that can have a wide variety of dimensions, and the dimensions used will depending upon the particular needs of the application in which the foam article will be used, and articles having all such dimensions are within the scope of the present invention.
  • the facing used in the present foam articles comprises one or more fibrous sheets or mats wherein the fibrous portion can be formed from a wide variety of materials, including for example, glass fibers (preferably impregnated with resin and/or polymers), other natural fibers (such as cellulose and other plant derived materials), mineral fibers (such as quartz), metal fibers or films, carbon fibers (preferably impregnated with or reinforced with one or more polymers, including thermoplastic polymer and/or thermoset polymers), synthetic fibers, such as polyesters (including fibers comprising furan-based polyesters, as disclosed for example in US 2015/0111450, which is incorporated herein by reference), polyethylenes, aramids, Kevlars, and any and all combinations of these.
  • the foam articles of the present invention have wide utility.
  • the present foam articles, including each of Foam Articles 1 - 3, have unexpected advantage in applications requiring low density and/or good compression and/or tensile and/or shear properties, and/or long-term stability, and/or sustainable sourcing, and/or being made from recycled material and being recyclable.
  • the present foam articles including each of Foam Articles 1 - 3, have unexpected advantage in: fluid energy transfer components, such as for example in wind and water energy transfer applications (e.g., wind turbine blades (shear webs, shells, cores, and nacelles) for transferring wind energy from fixed or mobile devices located in air, and vortex, tidal, oceans current oscillating hydrofoils and kites which recover water kinetic energy from fixed or mobile devices located in water); marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors); industrial low weight applications; automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft); and packaging applications.
  • wind and water energy transfer applications e.g., wind turbine blades (shear webs, shells, cores, and nacelles) for transferring wind energy from fixed or mobile devices located in air, and vortex, tidal, oceans current oscillating hydrofoils and kites which recover water kinetic energy from
  • the foam articles of the present invention may be used in a rotor blade 10 at any and all locations along the length of the blade from the blade root 30 to the blade tip 32 disposed opposite the blade root 30, and at any location along the body shell, including on the pressure side 34, on the suction side 36 and at all locations extending between leading edge 26 to the trailing edge 28 of the rotor blade 10.
  • the foam articles of the present invention may be used for all or part of a longitudinally extending structural components configured to provide increased stiffness, buckling resistance and/or strength to the rotor blade 10, such as, longitudinally extending spar caps 20, 22 configured to be engaged against the opposing inner surfaces 35, 37 of the pressure and suction sides 34, 36 of the rotor blade 10, as well as for one or more shear webs 24 disposed between the spar caps 20, 22 so as to form a beamdike configuration.
  • a longitudinally extending structural components configured to provide increased stiffness, buckling resistance and/or strength to the rotor blade 10, such as, longitudinally extending spar caps 20, 22 configured to be engaged against the opposing inner surfaces 35, 37 of the pressure and suction sides 34, 36 of the rotor blade 10, as well as for one or more shear webs 24 disposed between the spar caps 20, 22 so as to form a beamdike configuration.
  • the spar caps 20, 22 may generally be designed to resist the bending stresses and minimize blade tip deflection and/or other loads acting on the rotor blade 10 in a generally span-wise direction (a direction parallel to the span 23 of the rotor blade 16) during operation of a wind turbine 10; it is understood, however, that in other applications the spar cap may also be oriented at any angle transverse to the span-wise axis, including at an angle of about 90 degrees to the span-wise axis. Similarly, the spar caps 20, 22 may also be designed to resist the span-wise compression or tension occurring during operation of the wind turbine 6.
  • the root portions of the blade, as well as the spars and caps used in rotor blades may utilize to advantage such foams and foam articles.
  • Foam Use Table includes an identification of some of the preferred uses for some of the preferred articles of the present invention, wherein the column heading “Foam Article Number” refers to the Foam Article as identified above and the column heading Particular Foam refers to the Foams identified above.
  • a series of polymers were synthesized generally in accordance with the procedures described in Synthesis Examples 1 - 3 below.
  • the polymers produced in accordance with the present invention included homopolymers of PEF and copolymers of PEF with PET in various mole ratios. Homopolymers of PET were also produced for comparison purposes.
  • PEF foams in accordance with the present invention and PET foams for comparison purposes.
  • the polymers thus produced are identified in the following Table PFEx.
  • the series of PEF foams and reference PET foams were prepared using the highly preferred 1234ze(E) of the present invention as the blowing agent. Representative methods for forming the foams are reported in Foam Formation Examples 1 - 3 below.
  • the foams included foam densities that are grouped for convenience into the following ranges: (1) in the low density range of 0.060 g/cc up to 0.115 g/cc; (2) in a medium density range of greater than 0.115 g/cc up to 0.170 g/cc and (3) in a high density region of greater than 0.170 g/cc up to 0.250 g/cc.
  • a consistent set of processing conditions for a given range of comparable polymer properties were utilized. The details of each of these sets of experimental results are explained in the examples and tables which follow.
  • a series of foams were produced using the polymers described in Table PFEx above using foam processes which generally comprised placing approximately 1 gram of the polymer (as indicated in the following Table FFEx below) in a glass container, which was then loaded into a 60 cc volume autoclave and dried under vacuum for six (6) hours at an elevated temperature in the range of 130°C to 150°C. The dried polymer was then cooled to room temperature.
  • the blowing agent consisted of 1234ze(E). The blowing agent was pumped into the autoclave containing the dried polymer, and then the autoclave was heated to bring the polymer to a melt state.
  • the PET/blowing agent mixture was maintained in the melt state at the melt state pressure and temperature for about a period (designated below as the “Melt Time”, MTime) as indicated in the table (either 60 minutes or 15 minutes).
  • MTemp temperature
  • MP pressure
  • the temperature (MTemp) and pressure (MP) of the melt/blowing agent were then reduced over a period of about 5 - 15 minutes to pre-foaming temperature (PFT) and pre-foaming pressure (PFP), as indicated in Table FFEx.
  • PFT pre-foaming temperature
  • PFP pre-foaming pressure
  • the autoclave was then maintained at about this temperature and pressure for a period of about 30 minutes to ensure that the amount of blowing agent incorporated into the melt under such conditions reached equilibrium.
  • the temperature and pressure in the autoclave were then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
  • the conditions used including the amount of the blowing agent and the melt temperature and pressure, were determined after several tests, based on the ability to form acceptable foams with density values in the range of about 0.06 to 0.115 grams per cubic centimeter (g/cc) which are referred to for convenience in the tables below as low density foams, or in the range of greater than 0.115 to 0.250 g/cc, which are referred to for convenience in the tables below as high density foams.
  • Foam Formation Examples 1 - 3 Representative methods for forming the foams are reported in Foam Formation Examples 1 - 3 below, in which all foams used 1234ze(E) as the sole blowing agent.
  • Foam Formation Example 4 reports a series of foams made from PEF:PET copolymer and blowing agent 1233zd and 1336mzz, in addition to the preferred blowing agent 1234ze(E). These foams were prepared using the same general procedures as disclosed in Foam Formation Examples 1 -3.
  • foams made using 1234ze(E) were found to be unexpectedly superior to foams blown with other blowing agents other than 1234zd(E), acceptable foams were made and have substantial utility when the blowing agent comprises, or consists essentially of or consists of 1233zd(E) or 1336mzz(Z), as also revealed by the data reported in Foam Formation Example 3.
  • the foams of the present invention have superior strength characteristics, especially as measured by the value of the combined tensile strength and compressive strength, which combination also reflects superior shear strength properties.
  • the following charts show the trend line data for the combined value of the tensile strength and the compressive strength as a function of foam density in each of the low density region (see Figure 5), and high density region (see Figure 6) for the PEF homopolymer and the PEF :PET copolymers of the present invention in comparison to the PET homopolymers made using the same procedures.
  • the foams of the present invention in the low density region made from both PEF homopolymer (solid line) and the PEF:PETE copolymers (large dash line) of the present invention on average, produce a dramatically superior strength performance compared to the foams formed from PET homopolymer as a function of density over most of the low density range.
  • the PEF homopolymers and the PEF:PET copolymers of the present invention according to the present examples have on average a TS plus CS of about 2.4.
  • the foams of the present invention in the high density region made from both PEF homopolymer (solid line) and the PEF PETE copolymers (large dash line) of the present invention on average, also produce superior strength performance compared to the foams formed from PET homopolymer as a function of density over the substantially the entire medium density range.
  • the PEF homopolymers of the present invention according to the present examples have on average a TS plus CS of about 6. This represents an unexpected increase in strength of about 1.9 times compared to the average PET homopolymer performance (i.e., TS plus CS of 3.2).
  • a substantial advantage can also be achieved with the foams of the present invention made from the present PEF homopolymers and the PEF:PET copolymers compared to the foams formed from PET homopolymer by using the present foams to achieve the same strength as PET foam but with a substantially lower density.
  • the foams of the present invention provide important and unexpected advantages in connection with many uses. These advantages include the ability to achieve: (1) a superior strength for a given density; (2) reduced density, and hence a weight advantage, for a foam with the same density as previously used PET foam; and (3) a combination of superior strength and reduced density. Based on the average values illustrated in Figures 1 - 3, the following table provides specific examples of such advantages of replacing a PET foam with a specific density and/or strength (measured by TS plus CS) with a foam of the present invention:
  • a wind turbine generator having a configuration of the general type illustrated in Figures 1 - 3 hereof is constructed on land with a nacelle approximately 150 meters off the ground (referenced to the center-line of the nacelle).
  • the blade span for each of the blades from the hub axis to the blade tip is about 100 meters, resulting in a rotor diameter of about 200 meters.
  • the generator produces about 13 MW of electric power at peak design conditions.
  • Each blade includes faced PET foam, with about 30% by weight of the foam being a high density foam (i.e., density of 0.24 g/cc (prior to facing)) and with about 70% by weight of the PET foam being low density foam (i.e., density of 0.11 g/cc (prior to facing).
  • the total weight of all PET foam (not including the facing material) in the wind turbine is about 10% by weight of total blade weight.
  • Example 1A - 13 MW REDUDED WEIGHT WIND TURBINE GENERATOR MADE WITH PEF HOMOPOLYMER FOAM OF THE PRESENT INVENTION
  • a wind turbine generator having a configuration as described in Comparative Example 1 is constructed, except that the high density PET foam and/or the low density PET foam of Comparative Example 1 is replaced with foam of the present invention based on any one of Foams 1 - 4.
  • the high density PET foam and/or the low density PET foam of Comparative Example 1 is replaced by foam made from preferred PEF homopolymer foam blown with 1234ze as represented by the PEF Replacement Tables above and the trend lines in Figures 5 and 6 and/or by foam made from preferred PEFPET copolymer foam blown with 1234ze as represented by the PEFPET Replacement Tables above and the trend lines in Figures 5 and 6.
  • One option for making the replacement is to use, on an equal strength basis: (1) a PEF homopolymer represented by the PEF Replacement Tables above and the trend lines in Figure 5 to replace all of the low density PET; and (2) a PEFPET copolymer represented by the PEFPET Replacement Tables above and the trend lines in Figure 6 to replace all of the high density PET foam.
  • a PEF homopolymer according to the trendline in Figure 5 having a density of about 0.09 will have a strength that substantially matches the TS+CS strength as the low density PET foam. On average, this results in the ability to use a foam made from PEF homopolymer of the present invention that is about 22% lower in density, and hence about 22% lighter in weight, than the low density PET foam.
  • a PEFPET copolymer according to the trendline in Figure 6 having a density of about 0.16 will have a strength that substantially matches the TS+CS strength as the high density PET foam.
  • the unexpected reduction in blade weight achievable by using the foams of the present invention is substantial and commercially significant.
  • the reduced blade weight means that many other components of the wind turbine can be made smaller and/or lighter, which in turn has not only additional environmental benefits but also significant decrease in construction costs.
  • the nacelle of wind turbines is designed to be compatible with the blades, including to be of a size and weight to balance the torque created by the blades. In addition, this weight reduction will result in a cost savings for the tower design and construction costs.
  • the extent of weight reduction in the blade weight ranges from 2.5% to 3.95%, and for any given case those skilled in the art may select an option that does not provide the highest weight reduction in order to satisfy other requirements.
  • option 3 would be selected since it relies on 100% PEF homopolymer which can be sourced 100% from nonpetroleum products.
  • Option 4 may be of interest because it is expected that PEFPET copolymer may be available at a lower cost than PEF homopolymer.
  • a wind turbine generator having a configuration as described in Example 1 A is constructed, except that the PET foam core material of Comparative Example 1 A is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1336mzz, including as reported in Form Formation Example 4. Acceptable results are observed.
  • Example 1C - 13 MW WIND TURBINE GENERATOR MADE WITH PEF HOMOPOLYMER FOAM USING HFO-1233zd BLOWING AGENT
  • a wind turbine generator having a configuration as described in Example 1 A is constructed, except that the PET foam core material of Comparative Example 1 A is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1336mzz, including as reported in Form Formation Example 4. Acceptable results are observed.
  • a wind turbine generator having a configuration as described in Example 1 A is constructed, except that the PET foam core material of Comparative Example 1 A is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1224yd. Acceptable results are observed.
  • a wind turbine generator having a configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a foam of the present invention made from PEF polymer using ADR additive as described in Foam Formation Example 5. Acceptable results are observed.
  • Example 1 A wind turbine generator having a configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a foam of the present invention made from PEF polymer using PENTA additive as described in Foam Formation Example 5. Acceptable results are observed.
  • a wind turbine generator having a configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a foam of the present invention made from PEF polymer using PMDA plus talc additive as described in Foam Formation Example 5. Acceptable results are observed.
  • Example 2 17 MW WIND TURBINE GENERATOR MADE WITH THIN PEF HOMOPOLYMER FOAMS OF THE PRESENT INVENTION IN THE BLADE SHELL
  • a wind turbine generator having a configuration as described in Comparative Example 1 is made, except that the PET foam core is replaced with a PEF homopolymer foam of the present invention, including each of Foams 1 - 4, or foam made from PEF copolymer of the present invention, including Thermoplastic Polymer TPP1A - TPP22E.
  • the preferred homopolymeric foams of the present invention as represented by the PEF Replacement Tables above, show on average an approximate 1 .3 times higher tensile strength + compressive strength at about the same densities comparable to the density of the PET foam of Comparative Example 1.
  • the preferred PEF homopolymeric foams of the present invention are believed to have a shear strength advantage over PET foams at about this density.
  • shear strength is approximately the average of the tensile and compressive strength, and therefore the shear strength of the present copolymer foams have, on average, a shear strength that is about 1.3 times higher than that of the PET foam at a foam density of about 0.1 g/cc.
  • This 1.3 times advantage in shear strength is an unexpected and highly advantageous result, at least in part, because it enables the core foam thickness to be reduced by about 30 relative percent, as long as the flexural rigidity of the foam core is still acceptable, which is expected to be the case. This is indicated by the following calculations described in Chapter 3 of the Introduction to Sandwich Structures, Student Edition, 1995, Dan Zenkert.
  • T C T x /d
  • T x is the direct load in newtons (per width of the beam, which is 1cm in this case), causing bending of the beam (in this case the blade);
  • d is thickness of the core foam + skin, which is approximately equal to thickness of the core foam (in cm);
  • r c is the shear stress experienced by the core foam, as a result of the direct load. Since load here is in newton/cm, the stress becomes newton/cm 2 , which has the units of pressure. High shear strength, implies high shear stress (T C ), enabling lower core foam thickness, while still addressing the same direct load on the beam.
  • Example 3A 6 MW REDUCED WEIGHT WIND TURBINE GENERATOR
  • Example 3 HIGHER OUTPUT WIND TURBINE GENERATOR MADE WITH PEF HOMOPOLYMER IN THE ROOT AREA AND PET:PEF COPOLYMER AND/OR PEF HOMOPOLYMER FOAMS OF THE PRESENT INVENTION IN THE NON-ROOT OF THE BLADE SHELL
  • a wind turbine generator having a configuration as described in Comparative Example 1 is made, except that the combinations of PEF homopolymer and PEFPET copolymer of the present invention as described in Example 1 are used but for the purpose of increasing power output of the wind turbine instead of weight reduction.
  • use of various combinations of PEF homopolymers and/or PEFPET copolymers of the present invention allows a blade weight reduction in the range of 2.5% to about 4 % of the blade weight.
  • a weight reduction of 2.5% to 4% is expected to provide the blades to regain the 2.5% to 4% weight loss, but this time, with at least 1.1% to 1.8% longer blades, leading to from 2.4% to 3.8% more power.
  • the power data used for these calculations are shown in Figures 8 and 9.
  • advantage may also be achieved by using the same density of PEF or PETPEF foam of the present as was used in the PET foam invention but because of the increased strength of the present foam, it may be possible to improve blade design in various ways to achieve power improvements.
  • Example 3B - 6 MW WIND TURBINE GENERATOR MADE WITH PEF FOAM USING HFO-1336MZZ BLOWING AGENT
  • a wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1336mzz, including as reported in Form Formation Example 4. Acceptable results are observed.
  • Example 3C - 6 MW WIND TURBINE GENERATOR MADE WITH PEF HOMOPOLYMER FOAM USING HFO-1233zd BLOWING AGENT
  • a wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1336mzz, including as reported in Form Formation Example 4. Acceptable results are observed.
  • a wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention blown with a blowing agent consisting of HFO-1224yd. Acceptable results are observed.
  • Example 3E - 6 MW WIND TURBINE GENERATOR MADE WITH FOAM FORMED FROM PEF POLYMER MADE WITH ADR ADDITIVE
  • a wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention made from PEF polymer using ADR additive as described in Foam Formation Example 5. Acceptable results are observed.
  • Example 3A A wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention made from PEF polymer using PENTA additive as described in Foam Formation Example 5. Acceptable results are observed.
  • Example 3H - 6 MW WIND TURBINE GENERATOR MADE WITH FOAM FORMED FROM PEF POLYMER MADE WITH PENTA ADDITIVE
  • a wind turbine generator having a configuration as described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with a PEF polymer foam of the present invention made from PEF polymer using PMDA plus talc additive as described in Foam Formation Example 5. Acceptable results are observed.
  • Example 4 An aircraft using one or more of Foam Articles 1 - 3
  • An aircraft includes in one or more locations which require structural foam, including preferably at least a portion of one or more of the wing, fuselage, tail, doors, bulkheads, interiors and/or superstructures, contain at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the aircraft achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • Example 5 - A land vehicle using one or more of Foam Articles 1 - 3
  • An automobile includes in one or more locations which require structural foam, including preferably at least a portion of one or more of the side panels, floor panels, roof panels, engine compartments, battery compartments interiors and/or superstructures, contain at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the automobile achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • Example 6 A railway car using one or more of Foam Articles 1 - 3
  • a railway car includes in one or more locations which require structural foam, including preferably at least a portion of one or more of the side panels, floor panels, roof panels and superstructures, contain at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the railway car achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • Example? - A building using one or more of Foam Articles 1 - 3
  • a building structure that includes in one or more locations which require structural foam, including preferably at least a portion of one or more of the wall panels, floor structure and roof structure and other structures in the building, contain at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the building achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • Example 8 Packaging using one or more of Foam Articles 1 - 3
  • Packaging preferably in the form of boxes, inserts, separators, envelops and the like, that includes in one or more locations which require structural foam, contains at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the building achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • Example 9 Sporting Goods using one or more of Foam Articles 1 - 3
  • a sporting good including preferably a tennis racket, a skate board, a water or snow ski, and the like, that includes in one or more locations which require structural foam, contains at least one foam article of the present invention, including on or more of each of Foam Articles 1 - 3.
  • the sporting good achieves: (1) a lighter foam weight than previously used structural foam articles, preferably a weight that is at least about 2% less than the weight of the previously used foam; (2) an advantage in size and/or performance compared to using the same foam weight as previously used structural foam; and/or (3) a combination of (1) and (2).
  • a PEF homopolymer having a molecular weight of 41.2 kg/mol 1 was formed by esterification and polycondensation of 75 grams of 2,5-furandicarboxylic acid (FDCA) with 55 grams of mono-ethylene glycol (EG).
  • FDCA 2,5-furandicarboxylic acid
  • EG mono-ethylene glycol
  • the reactants were added to a 500-mL cylindrical steel reactor equipped with an overhead stirrer and a distillation/condensation apparatus. After pulling vacuum and back filling with nitrogen, 0.228 gram of titanium (IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a 180°C salt bath and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes at this temperature under nitrogen, vacuum was started.
  • FDCA 2,5-furandicarboxylic acid
  • EG mono-ethylene glycol
  • a 75 kg/mol PEF homopolymer was formed by esterification and polycondensation of 350 grams of 2,5-furandicarboxylic acid (FDCA) with 279 grams of mono-ethylene glycol (EG).
  • FDCA 2,5-furandicarboxylic acid
  • EG mono-ethylene glycol
  • the reactants were added to a 1 -liter cylindrical steel reactor equipped with an overhead stirrer and a distillation/condensation apparatus. After pulling vacuum and back filling with nitrogen, 0.228 gram of titanium (IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a 180°C salt bath and overhead
  • molecular weight as determined and referenced herein refers to molecular weight determination by diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR) as per the description contained in “Application of 1 H DOSY NMR in Measurement of Polystyrene Molecular Weights,” VNll Journal of Science: Natural Sciences and Technology, Vol. 36, No. 2 (2020) 16-21 June 2020, Nam et a , except for differences in the solvents used.
  • the reference above used 3 mg of polystyrene and 0.5 ml of deuterated chloroform.
  • NMR measurements were made with the dissolved portion of 2-3 mg of polymer in a 0.6 ml mixture of 50 vol% deuterated chloroform + 50 vol% trifluoroacetic acid. mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes at this temperature under nitrogen, vacuum was started. After 40 minutes under vacuum, the temperature was increased to 230°C and was continued for 1 hour. Under a stream of nitrogen, PMDA (2.73 g - 0.7% by weight) was slowly added over the span of about 5 minutes. An additional 30 minutes of mixing at temperature were allowed before stopping the reaction. To perform SSP, an aliquot (30 g) of the product was ground and heated at 180°C under vacuum for 3 days on a rotary evaporator to produce the PEF homopolymer with a molecular weight of 75 kg/mole .
  • a 96,078 g/mol MW polymer is made by combining 75 grams of 2,5- furandicarboxylic acid (FDCA) with 55 grams of mono-ethylene glycol (EG).
  • FDCA 2,5- furandicarboxylic acid
  • EG mono-ethylene glycol
  • the reactants were added to a 500-mL cylindrical steel reactor equipped with an overhead stirrer and a distillation/condensation apparatus. After pulling vacuum and back filling with nitrogen, 0.228 gram of titanium (IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a 180°C salt bath and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes at this temperature under nitrogen, vacuum was started.
  • FDCA 2,5- furandicarboxylic acid
  • EG mono-ethylene glycol
  • PEF Oligomers were prepared by adding 109 grams of EG and 0.45 grams of sodium carbonate to a 500 ml cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated until boiling in at salt bath at 230 °C. An aliquot of PEF (160 grams) from the above step was added. The mixture was allowed to react under reflux for 2 hours until the reaction was stopped. The resulting mixture are the PEF oligomers.
  • PET Oligomers were prepared by adding, 103 grams of EG and 0.45 gram of sodium carbonate to a 500 ml cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated in at salt bath at 230 °C. Then 160 grams of commercially available recycled PET flake were added. The mixture was allowed to react under reflux for 2 hours until the reaction was stopped. The result was a PET oligomer mixture.
  • the co-polymer was made by quickly adding 12.0 grams of the PEF oligomers and 111.7 grams of the PET oligomers to a 500mL cylindrical steel reactor equipped with an overhead stirrer and a distillation/condensation apparatus that was immersed in a 220°C salt bath, followed by adding 0.9083 grams of Ti(IV) isopropoxide. Shortly thereafter ( ⁇ 2 min), vacuum was applied to remove EG. After 40 minutes, the temperature was increased to 270°C, and the contents of the reactor were allowed to remain under vacuum for 40 minutes. Under a N2 atmosphere, 0.483 gram of PMDA was slowly added. An additional 30 minutes of mixing at temperature were allowed before stopping the reaction.
  • Solid state polymerization was conducted by grinding an aliquot (30g) of the above product and then heating at 180°C under vacuum for 3 days on a rotary evaporator to produce the PET9:PEF1 copolymer with a PET molecular weight of 117.9 kg/mole.
  • ADR 2 and PENTA were used to replace PMDA alone.
  • ADR 4468 is a trade name for 2,3-Epoxypropyl methacrylate chain extender sold by BASF under the Joncryl family of trademarks. Synthesis Examples 4A - 3D - PET HOMOPOLYMER PREPARATION AT MOLECULAR WEIGHTS IN THE RANGE OF 80 - 96 KG/MOL AND CRYSTALLINTY OF 32 - 43 WITH PMDA
  • PET homopolymers were prepared by polycondensation yielding polymer products having a range of molecular size from about 80 kg/mol to about of 96 kg/mol using the procedures describe in Synthesis Example 1 above an variations thereof to achieve the polymer with a molecular weight as indicted in SyEx4 below.
  • PETCI PETCI
  • PETC2 PETC3 and PETC
  • Table SyEx4 The PET polymers are designated herein as PETCI, PETC2, PETC3 and PETC and were tested and found to have the characteristics as reported in Table SyEx4 below:
  • each of the PET homopolymers was produced utilizing the preferred high crystallinity aspects of the present invention.
  • the temperature and pressure of the melt/blowing agent were then reduced over a period of about 5 - 15 minutes to prefoaming temperature and pre-foaming pressure, as indicted in tables above.
  • the autoclave was then maintained at about this temperature and pressure for a period of about 30 minutes to ensure that the amount of blowing agent incorporated into the melt under such conditions reached equilibrium.
  • the conditions used including the amount of the blowing agent and the melt temperature and pressure, were determined after several tests, based on the ability to form acceptable foams with RFD values in the range of about 0.05 to about 0.25.
  • the temperature and pressure in the autoclave were then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
  • the PET foams thus produced have the properties identified in Table FFeX - Low Density Foams and Table FFeX - High Density Foams above.
  • One foam was made using PEF1 and four foams were made using PEF2 identified in Table FFeX - Low Density Foams and Table FFeX - High Density Foams above and, as described herein, using foaming processes that were designed using the same criteria as described in SyExCl above.
  • the foams thus produced were tested and found to have the properties as reported in in Table FFeX - Low Density Foams and Table FFeX - High Density Foams above and as shown in Table FFEx2 below.
  • PET9PEF1-EX3A WITH TRANS1234ZE BLOWING AGENT AND PENTA, ADR AND PMDA+TALC ADDITIVES
  • Foams were made from PET9PEF1 as described above in Synthesis Example 4 above using foaming processes that were designed using the same criteria as described in Foam Formation Examples 1 - 3. The foams thus produced were tested and found to have the properties as reported in Table FFEx5 below:
  • PET:PEF foams according to the present invention generally possess superior strength characteristics when the preferred blowing agent comprises, or consists essentially of or consists of 1234ze(E) is used with a variety of polymerization additives.

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Abstract

L'invention concerne des articles en mousse comprenant une mousse thermoplastique à cellules fermées ayant au moins une première surface et comprenant : (i) des parois cellulaires polymères thermoplastiques comprenant au moins environ 0,5 % en poids de fractions furanoate d'éthylène et éventuellement une ou plusieurs fractions co-monomères ; (ii) un agent gonflant contenu dans au moins une partie desdites cellules fermées ; et un matériau différent de ladite mousse thermoplastique à cellules fermées fixé et/ou intégré à au moins une partie de ladite première surface en mousse.
EP23808422.2A 2022-05-19 2023-05-19 Mousses thermoplastiques et utilisations dans des applications nécessitant une résistance et un poids léger Pending EP4508122A4 (fr)

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US4323528A (en) * 1980-08-07 1982-04-06 Valcour Imprinted Papers, Inc. Method and apparatus for making large size, low density, elongated thermoplastic cellular bodies
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CN110799572A (zh) * 2017-06-07 2020-02-14 Sabic环球技术有限责任公司 可发泡的热塑性聚酯共聚物
CN108410000B (zh) * 2018-04-20 2020-09-18 中国科学院宁波材料技术与工程研究所 2,5-呋喃二甲酸基聚酯发泡材料及其制备方法
BE1028470B1 (nl) * 2020-07-10 2022-02-08 De Roeve Koen Thermoplastisch composiet element met verbeterde weerstand tegen delaminatie
CA3228702A1 (fr) * 2021-08-16 2023-02-23 Hayim Abrevaya Compositions thermoplastiques expansibles, mousses thermoplastiques et leurs procedes de fabrication
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