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WO2025156277A1 - Élastomères polyoléfiniques (poe) pour des encapsulants photovoltaïques et leurs procédés de fabrication - Google Patents

Élastomères polyoléfiniques (poe) pour des encapsulants photovoltaïques et leurs procédés de fabrication

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Publication number
WO2025156277A1
WO2025156277A1 PCT/CN2024/074294 CN2024074294W WO2025156277A1 WO 2025156277 A1 WO2025156277 A1 WO 2025156277A1 CN 2024074294 W CN2024074294 W CN 2024074294W WO 2025156277 A1 WO2025156277 A1 WO 2025156277A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin elastomer
cross
independently
ethylene
formulation
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
PCT/CN2024/074294
Other languages
English (en)
Inventor
Gaoxiang WU
Yabin Sun
Jeffrey C. Munro
Jie XIONG
Johnathan E. DELORBE
Thomas Wesley KARJALA
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to PCT/CN2024/074294 priority Critical patent/WO2025156277A1/fr
Priority to PCT/CN2025/075205 priority patent/WO2025157309A1/fr
Priority to PCT/CN2025/075191 priority patent/WO2025157305A1/fr
Priority to PCT/CN2025/075199 priority patent/WO2025157307A1/fr
Priority to PCT/CN2025/075221 priority patent/WO2025157311A1/fr
Priority to PCT/CN2025/075183 priority patent/WO2025157303A1/fr
Priority to PCT/CN2025/075187 priority patent/WO2025157304A1/fr
Publication of WO2025156277A1 publication Critical patent/WO2025156277A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene

Definitions

  • Embodiments of the present disclosure generally relate to polyolefin elastomers and specifically relate to polyolefin elastomers used in photovoltaic encapsulants.
  • Materials designed for photovoltaic encapsulants must satisfy many requirements. In order to prevent movement of electrical components and wiring, within a photovoltaic module, polymeric encapsulating materials must not flow significantly at temperatures up to 85°C. One way to accomplish this, is to use a semicrystalline polymer with a melting point above this temperature. However, other encapsulating material requirements, such as high optical clarity and low modulus, are optimized with low-crystallinity polymers.
  • a low-crystallinity polymer such as an ethylene-vinyl acetate copolymer (EVA) or a polyolefin elastomer (POE) , such as an ENGAGE TM Polyolefin Elastomer
  • EVA ethylene-vinyl acetate copolymer
  • POE polyolefin elastomer
  • the film extrusion process must be conducted at a low temperature, in order to prevent the peroxide from decomposing and initiating the crosslinking reaction in the extruder.
  • Heat generated during extrusion is related to the rate of extrusion and the polymer viscosity; high viscosity and high extrusion rates generate more heat. Therefore, to extrude a “peroxide-curing” encapsulant film, a low viscosity resin, extruded at low rates, is preferred.
  • low extrusion rates are economically disadvantageous, and low viscosity is typically achieved via the use of a low molecular weight resin.
  • Low molecular weight resins cannot be cross-linked efficiently, and require a higher loading of peroxide in the curing formulation or longer times in the module lamination process, in order to reach the necessary level of crosslinking.
  • the excessive amount of peroxide or coagent additives mixed with POE can lead to migration to the surface due to low compatibility of the additives with POE materials, leading to slippery film surface, which is considered as a major shortcoming of the POE based encapsulant compared to EVA based or EVA-POE-EVA multilayer based film designs.
  • Embodiments of the present disclosure meet this need via polyolefin elastomers having high vinyl level on the polymer chain-end, a low oligomer level, and a high level of long chain branching (LCB) .
  • These polyolefin elastomers optimize the balance of peroxide curing, processability, and the possibility of using lower curative additive levels to reach the required peroxide curing response.
  • a polyolefin elastomer comprises the polymerized reaction product of ethylene monomer and at least one C 4 -C 12 alpha-olefin comonomer, the polyolefin elastomer having: a density from 0.860 to 0.900 g/cc; a melt index (I 2 ) of 0.5 to 30 dg/min, wherein I 2 is measured according to ASTM D1238 (190 °C, 2.16 Kg) ; an I 10 /I 2 greater than or equal to 8, wherein I 10 is measured according to ASTM D1238 (190 °C, 10 Kg) ; greater than or equal to 0.2 vinyls per 1000 carbons; the percentage of vinyls in the total unsaturation is greater than or equal to 50%; and an oligomer level less than 5000 ppm.
  • Further embodiments are directed to a process for preparing ethylene-based polymers, for example, the polyolefin elastomers of the present disclosure.
  • the process comprises solution polymerizing ethylene, and optionally an ⁇ -olefin comonomer in the presence of a procatalyst having the following Structure (I) :
  • M is Zr or Hf, the metal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is an independently chosen monodentate ligand; the procatalyst is overall charge-neutral; at least one of R 1 and R 16 are selected from structure (II) , structure (III) , and structure (IV) :
  • R 3 and R 14 are independently C 1 -C 40 hydrocarbyl or hydrogen
  • R 6 and R 11 are independently C 1 -C 40 hydrocarbyl or hydrogen
  • R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 are independently selected from the group consisting of a C 1 -C 40 hydrocarbyl, C 1 -C 40 heterohydrocarbyl, -Si (R C ) 3, halogen atom, hydrogen atom, and combinations thereof;
  • R 17 and R 18 are independently C 1 -C 3 hydrocarbylene
  • R 19 and R 20 are independently C 1 -C 40 hydrocarbyl or hydrogen.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer includes the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) , and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer.
  • ppm amounts
  • interpolymer refers to a polymer prepared by the polymerization of at least two different types of monomers.
  • the term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
  • polyolefin refers to a polymer that comprises, in polymerized form, 50 wt. %or a majority weight percent of an olefin, such as ethylene or propylene (based on the weight of the polymer) , and optionally may comprise one or more comonomers.
  • ethylene-based polymer or “polyethylene” as used herein, refers to a polymer that comprises, in polymerized form, 50 wt. %or a majority weight percent of ethylene (based on the weight of the polymer) , and optionally may comprise one or more comonomers.
  • ethylene/alpha-olefin copolymer refers to a copolymer that comprises, in polymerized form, 50 wt. %or a majority weight percent of ethylene (based on the weight of the copolymer) , and an alpha-olefin, as the only two monomer types.
  • the ethylene/alpha-olefin copolymer is a random copolymer (i.e., comprises a random distribution of its monomeric constituents) .
  • unimodal refers to a molecular weight distribution (MWD) indicated by a Gel Permeation Chromatography (GPC) curve that exhibits a single peak, which is defined by a single positive inflection point where derivative values of the GPC curve for the MWD go from positive to negative as the log (molecular weight) increases within a range from 2 to 8, further 3 to 7.
  • the resin has Mw/Mn less than about 3.5, further less than 2.8. More preferably, resin composition is the result of a single reactor, single catalyst polymerization process.
  • cross-linked composition or “cross-linked polyolefin elastomer” as used herein, refers to a composition that has a network structure due to the formation of chemical bonds between polymer chains. The degree of formation of this network structure is indicated by an increase in the “MH-ML” differential, relative to the non-cross-linked composition.
  • a cross-linked composition typically has a gel content ⁇ 50 wt%, further ⁇ 60 wt%, further ⁇ 70 wt%, further ⁇ 80 wt%, based on the weight of the cross-linked composition. See Gel Test below.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term ′′consisting of” excludes any component, step or procedure, not specifically delineated or listed.
  • Embodiments of the present disclosure are directed to polyolefin elastomers comprising the polymerized reaction product of ethylene monomer and at least one C 4 -C 12 alpha-olefin comonomer.
  • the polyolefin elastomer comprises: a density from 0.860 to 0.900 g/cc; a melt index (I 2 ) of 0.5 to 30 dg/min, wherein I 2 is measured according to ASTM D1238 (190 °C, 2.16 Kg) ; an I 10 /I 2 greater than or equal to 8, wherein I 10 is measured according to ASTM D1238 (190 °C, 10 Kg) ; greater than or equal to 0.2 vinyls per 1000 carbons; the percentage of vinyls in the total unsaturation is greater than or equal to 50%; and an oligomer level less than 5000 ppm.
  • the polyolefin elastomer may comprise an ethylene-based polymer comprising the polymerized reaction product of ethylene and a C 4 -C 12 alpha-olefin comonomer.
  • the ethylene-based polymer is an ethylene/alpha-olefin random copolymer.
  • the ethylene-based polymer is a unimodal ethylene/alpha-olefin random copolymer.
  • the C 4 -C 12 alpha-olefin comonomer may include various alpha-olefin comonomers, for example, 1-butene, 1-hexene, and 1-octene.
  • the alpha-olefin comonomer comprises 1-octene.
  • the polyolefin elastomer may include a density of 0.860 to 0.900 g/cc, from 0.860 to 0.880 g/cc, or from 0.865 to 0.875 g/cc.
  • the polyolefin elastomer may include a melt index (I 2 ) of 0.5 to 30 dg/min wherein I 2 is measured according to ASTM D1238 (190 °C, 2.16 Kg) , and in further embodiments, may include an I 2 from 1.0 to 25 dg/min, from 2.0 to 20 dg/min, or from 3 to 18 dg/min.
  • I 2 melt index
  • the I 2 may have ranges extending from a lower limit of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, or 12.0 dg/min to an upper limit of 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0 18.0, 20.0, 25.0, or 30.0 dg/min.
  • the polyolefin elastomer may include an I 10 /I 2 greater than or equal to 8, wherein I 10 is measured according to ASTM D1238 (190 °C, 10 Kg) , and in further embodiments, may include an I 10 /I 2 of 8 to 20, from 8 to 15, from 8 to 12, or from 8 to 11, or from 9 to 11, or from 9.5 to 11. Without being limited to theory, this I 10 /I 2 range correlates to increased long chain branching which aids in the processability of the POE resin.
  • the polyolefin elastomer may have a high vinyl unsaturation as demonstrated by having greater than or equal to 0.2 vinyls per 1000 carbons, and in further embodiments may include 0.2 to 1 vinyls per 1000 carbons, from 0.2 to 0.8 vinyls per 1000 carbons, or from 0.2 to 0.6 vinyls per 1000 carbons.
  • the polyolefin elastomer may include greater than 0.2 unsaturations per 1000 carbons, or greater than 0.3 unsaturations per 1000 carbons, and in further embodiments may include from 0.35 to 2 unsaturations per 1000 carbons, from 0.35 to 1 unsaturations per 1000 carbons, or from 0.40 to 0.80 unsaturations per 1000 carbons.
  • the percentage of vinyls in the total unsaturation of the polyolefin elastomer is at least 50%, at least 55%, at least 60%, at least 65%, or at least 70%.
  • the polyolefin elastomer may have an oligomer level less than 5000 ppm, and in further embodiments may have an oligomer level less than 4500 ppm, less than 4000 ppm, less than 3500 ppm, less than 3000 ppm, or less than 2500 ppm, less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 500 ppm, less than 250 ppm, or less than 200 ppm.
  • the present polyolefin elastomer have a high vinyl level on the chain-end and low oligomer level due to selection of catalyst and process conditions. In polymers with high vinyl level and high oligomer level, there can be a high level of oligomers (low Mw components) with vinyl chain ends, which result in low cross-linking efficiency.
  • the polyolefin elastomers may have a number average molecular weight (Mn) of 20 to 30 kg/mol, or from 22 to 28 kg/mol, wherein Mn is measured in accordance with conventional Gel Permeation Chromatography (GPC) .
  • Mn number average molecular weight
  • the polyolefin elastomers may have a Mw/Mn of 2.0 to 3.0, from 2.4 to 3.0, or from 2.5 to 2.6, wherein Mw (weight average molecular weight) is measured in accordance with conventional GPC.
  • the polyolefin elastomer may have a rheology ratio (V 0.1 /V 100 ) of greater than 3 wherein V 0.1 is the viscosity at 190 °C at an angular frequency of 0.1 radians/second, V 100 is the viscosity at 190 °C at an angular frequency of 100 radians/second.
  • the rheology ratio may be greater than 1.5, greater than 2 or greater than 4.
  • the rheology of the polyolefin elastomer may be characterized by the following equation: (V 0.1 /V 100 ) *I 2 0.5 , which further accounts for the effect of melt index.
  • the polyolefin elastomer may have a value of greater than 7.5 (dg/min) 0.5 , greater than 8 (dg/min) 0.5 , greater than 10 (dg/min) 0.5 , greater than 14 (dg/min) 0.5 , greater than 16 (dg/min) 0.5 , greater than 18 (dg/min) 0.5 , or greater than 20 (dg/min) 0.5 .
  • the present disclosure is also directed to cross-linkable polyolefin elastomer formulations, which comprise the polyolefin elastomer and a curing package.
  • the curing package may comprise organic peroxide.
  • the curing package may also comprise crosslinking coagent.
  • the cross-linking package may also comprise silane coupling agent.
  • Useful peroxides include, but are not limited to, peroxycarbonates, such as, for example, tert-amylperoxy-2-ethylhexyl carbonate (TAEC) ; and peroxyketals, such as, for example, 1, 1-di (tert-amylperoxy) cyclohexane.
  • peroxycarbonates such as, for example, tert-amylperoxy-2-ethylhexyl carbonate (TAEC)
  • TAEC tert-amylperoxy-2-ethylhexyl carbonate
  • peroxyketals such as, for example, 1, 1-di (tert-amylperoxy) cyclohexane.
  • organic peroxides may include t-butylperoxyisopropyl carbonate; t-butylperoxy-2-ethylhexyl carbonate (TBEC) ; tert-Amylperoxy 2-ethylhexyl carbonate (TAEC) ; t-butylperoxyacetate; t-butylperoxybenzoate; dicumyl peroxide; 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane; di-t-butyl peroxide; 2, 5-dimethyl-2, 5-di- (t-butyl-peroxy) hexyne-3; 1, 1-di- (t-butylperoxy) -3, 3, 5-trimethyl-cyclohexane; 1, 1-di- (t-butylperoxy) -cyclohexane; methyl ethyl ketone peroxide; 2, 5-dimethyl-hexyl-2, 5-diperoxy
  • the silane coupling agents may include one or more alkoxysilane coupling agents, such as vinyltrimethoxy-silane (VTMS) , 3- (trimethoxysilyl) -propyl-methacrylate (VMMS) , tetraethoxysilane (TEOS) or combinations thereof.
  • VTMS vinyltrimethoxy-silane
  • VMMS 3- (trimethoxysilyl) -propyl-methacrylate
  • TEOS tetraethoxysilane
  • the silane coupling agent comprises VTMS, VMMS, or combinations thereof.
  • crosslinking coagents are also contemplated. These may include crosslinking coagents, such as triallyl isocyanurate (TAIC) , triallyl phosphate (TAP) . triallyl cyanurate (TAC) , triallyl trimellitate (TATM) , 1, 3, 5, 7-Tetravinyl-1, 3, 5, 7-tetramethylcyclotetrasiloxane (vinyl D4) .
  • crosslinking coagents such as triallyl isocyanurate (TAIC) , triallyl phosphate (TAP) .
  • TAC triallyl cyanurate
  • TTM triallyl trimellitate
  • TMPTA trimethylolpropane triacylate
  • TMPTMA trimethylolpropane trimethylacrylate
  • 1, 6-hexanediol diacrylate pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate
  • 2-hydroxyethyl) isocyanurate triacrylate trivinyl cyclohexane (TVCH) , or combinations thereof.
  • the polyolefin elastomer of the present disclosure may allow for lower amounts of the curing package to be utilized in the cross-linkable polyolefin elastomer formulations, or cross-linkable polyolefin elastomers produced therefrom.
  • the curing package may be present in amounts of 0.2 to 3.0 wt. %in the cross-linkable polyolefin elastomer formulation, or in other embodiments from 1.0 to 2.0 wt. %, or from 1.5 to 2.0 wt. %of the cross-linkable polyolefin elastomer formulation.
  • the cross-linkable polyolefin elastomer formulation comprises 85 to 99.5 wt. %polyolefin elastomer, from 90 to 99.5 wt. %polyolefin elastomer, from 98 to 99 wt. %polyolefin elastomer.
  • the organic peroxide may be present in amounts of 0.1 to 2.0 wt. %in the cross-linkable polyolefin elastomer formulation, or in other embodiments from 0.2 to 1.0 wt. %, or from 0.5 to 1.0 wt. %of the cross-linkable polyolefin elastomer formulation.
  • the silane coupling agent may be present in amounts of 0.05 to 1.0 wt. %in the cross-linkable polyolefin elastomer formulation, or in other embodiments from 0.1 to 0.5 wt. %, or from 0.1 to 0.3 wt. %of the cross-linkable polyolefin elastomer formulation.
  • the cross-linking co-agent may be present in amounts of 0.1 to 2.0 wt. %in the cross-linkable polyolefin elastomer formulation, or in other embodiments from 0.2 to 1.0 wt. %, or from 0.5 to 1.0 wt. %of the cross-linkable polyolefin elastomer formulation.
  • Additional additives or filler may include UV absorbers and/or stabilizers, for example, hindere d amine light stabilizers such as TINUVIN 770; TiO 2 , one or more anti-oxidants; processing aids, such as fluoropolymers, polydimethylsiloxane (PDMS) , ultra-high molecular weight PDMS; ion scavengers, anti-potential induced degradation (PID) agents; other siloxanes; fumed silica, nano-Al 2 O 3 , nano-clay, and one or more other fillers.
  • UV absorbers and/or stabilizers for example, hindere d amine light stabilizers such as TINUVIN 770; TiO 2 , one or more anti-oxidants
  • processing aids such as fluoropolymers, polydimethylsiloxane (PDMS) , ultra-high molecular weight PDMS; ion scavengers, anti-potential induced degradation (PID
  • an additive is present in an amount ⁇ 0.20 wt%, or ⁇ 0.40 wt%, or ⁇ 0.60 wt%, or ⁇ 0.80 wt%, and/or ⁇ 5.0 wt%, or ⁇ 4.0 wt%, or ⁇ 3.0 wt%, or ⁇ 2.0 wt%, or ⁇ 1.5 wt%, or ⁇ 1.0 wt%, based on the weight of the composition.
  • the cross-linked polyolefin elastomer may be produced from the cross-linkable polyolefin elastomer formulation via curing processes known to thos e skilled in the art.
  • the curing may be initiated by heat, irradiation, electron beam radiation, or ultraviolet (UV) radiation.
  • the cross-linked polyolefin elastomer may be incorporated in various articles. These may be included in films, for example, in multilayer films.
  • Multilayer films may comprise layers of the same or different compositions.
  • the polymer used in each layer may differ or the level of curative components in the composition of each layer may differ.
  • the multilayer films may comprise two or more layers, for example 2 to 5 layers.
  • An exemplary multilayer film is an EVA-POE-EVA three layer film where the polyolefin elastomer of this invention is used in the middle POE layer.
  • the article may be an encapsulant for a photovoltaic module.
  • the process for preparing an ethylene-based polymer comprises solution polymerizing ethylene, and optionally an ⁇ -olefin comonomer in the presence of a procatalyst having the following Structure (I) :
  • M is Zr or Hf, the metal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is an independently chosen monodentate ligand; the procatalyst is overall charge-neutral;
  • R 1 and R 16 are selected from structure (II) , structure (III) , and structure (IV) :
  • R 3 and R 14 are independently C 1 -C 40 hydrocarbyl or hydrogen
  • R 6 and R 11 are independently C 1 -C 40 hydrocarbyl or hydrogen
  • R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 are independently selected from the group consisting of a C 1 -C 40 hydrocarbyl, C 1 -C 40 heterohydrocarbyl, -Si (R C ) 3, halogen atom, hydrogen atom, and combinations thereof;
  • R 17 and R 18 are independently C 1 -C 3 hydrocarbylene
  • R 19 and R 20 are independently C 1 -C 40 hydrocarbyl or hydrogen.
  • M is Zr.
  • R 1 and R 16 are each structure (III) :
  • R 41–48 are independently chosen from –H or C 1 -C 6 alkyl. In yet another embodiment, R 41–48 are–H.
  • R 3 and R 14 may be C 1 -C 12 alkyl, C 6 -C 12 alkyl, or C 8 -C 12 alkyl.
  • R 6 and R 11 may each C 1 -C 12 alkyl, C 6 -C 12 alkyl, or C 6 -C 10 alkyl.
  • R 3 , R 6, R 11, and R 14 are each C 6 -C 11 alkyl.
  • R 17 and R 18 may each be -CH 2 -.
  • R 19 and R 20 may independently be C 2 -C 10 alkyl, C 2 -C 6 alkyl, from C 2 -C 4 alkyl, or C 3 alkyl.
  • R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 and R 15 are hydrogen atoms.
  • the procatalyst is free of halogens.
  • the polymerizing may occur in one reactor or multiple reactors.
  • Various reactors are considered suitable, for example, loop reactors or continuous stirred tank reactors (CSTR) .
  • the above described catalyst activates the solution polymerization process in a single reactor.
  • the solution polymerization process may occur at a temperature above 150°C, above 170°C, or above 180°C.
  • the solution polymerization process may occur at a pressure above 30 bar (3 MPa) , or above 40 bar (4 MPa) .
  • Various hydrocarbon solvents are considered suitable for the solution polymerization.
  • the solvent is an isoparaffinic solvent.
  • the polymerizing may also occur in the presence of a cocatalyst, of which various compositions are considered suitable.
  • the cocatalyst comprises an alumoxane.
  • the cocatalyst is a methylalumoxane (MMAO) .
  • the ethylene-based polymer produced by the solution polymerization process is an ethylene/alpha-olefin copolymer, for example, an ethylene/alpha-olefin random copolymer.
  • the alpha-olefin comonomers include the C 4 -C 12 comonomers described above.
  • the produced ethylene-based polymer may be the polyolefin elastomer as defined above, specifically, a polyolefin elastomer comprising: a density from 0.860 to 0.900 g/cc; a melt index (I 2 ) of 0.5 to 30 dg/min, wherein I 2 is measured according to ASTM D1238 (190 °C, 2.16 Kg) ; an I 10 /I 2 greater than or equal to 8, wherein I 10 is measured according to ASTM D1238 (190 °C, 10 Kg) ; greater than or equal to 0.2 vinyls per 1000 carbons; the percentage of vinyls in the total unsaturation is greater than or equal to 50%; and an oligomer level less than 5000 ppm.
  • a polyolefin elastomer comprising: a density from 0.860 to 0.900 g/cc; a melt index (I 2 ) of 0.5 to 30 dg/min, wherein I 2 is measured according to ASTM D
  • Density is measured in accordance with ASTM D792, and expressed in grams/cm 3 (g/cc or g/cm 3 ) .
  • the Melt Index (I 2 ) is measured in accordance with ASTM D-1238, (190 °C/2.16 kg) .
  • the Melt Index (I 10 ) is measured in accordance with ASTM D-1238, (190 °C/10 kg) .
  • the chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) .
  • the autosampler oven compartment was set at 160° Celsius and the column and detector compartment were set at 150° Celsius.
  • the columns used were 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns.
  • the chromatographic solvent used was 1, 2, 4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT) .
  • BHT butylated hydroxytoluene
  • the solvent source was nitrogen sparged.
  • the injection volume used was 200 microliters and the flow rate was 1.0 milliliters/minute.
  • Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights.
  • the standards were purchased from Agilent Technologies.
  • the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000.
  • the polystyrene standards were pre-dissolved at 80 °C with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160 °C for 30 minutes.
  • M is the molecular weight
  • A has a value of 0.4163 and B is equal to 1.0.
  • a fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points.
  • the total plate count of the GPC column set was performed with decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system.
  • the plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns.
  • Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hours at 160°Celsius under “low speed” shaking.
  • Mn (GPC) , Mw (GPC) , and Mz (GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2-4, using PolymerChar GPCOne TM software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i) , and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1.
  • a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system.
  • This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate (nominal) ) for each sample by RV alignment of the respective decane peak within the sample (RV (FM Sample) ) to that of the decane peak within the narrow standards calibration (RV (FM Calibrated) ) . Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate (effective) ) for the entire run.
  • the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the PolymerChar GPC One TM Software. Acceptable flowrate correction is such that the effective flowrate should be within +/-0.5%of the nominal flowrate.
  • Flowrate (effective) Flowrate (nominal) * (RV (FM Calibrated) /RV (FM Sample) ) (EQ5)
  • Cure characteristics were measured using an Alpha Technologies Moving Die Rheometer (MDR) 2000 E, according to ASTM D5289, with a 0.5 ° arc.
  • MDR Moving Die Rheometer
  • the MDR was loaded with approximately 5 g of the formulated materials.
  • the MDR was run for 30 minutes, at 150°C.
  • DCP dicumyl peroxide
  • the MDR was run for 20 minutes, at 180°C.
  • the “time vs torque” profile was generated over the given interval in all cases.
  • the key parameter used to understand the curing degree of the formulation is the MH-ML (dNm) : the higher MH-ML value correlated to a more cross-linked polymer network.
  • MH (dNm) referred to the maximum torque exerted by the MDR during the testing interval
  • ML (dNm) referred to the minimum torque exerted by the MDR during the testing interval.
  • the sample extract, DCM blank, and certified reference standard (Ultra Scientific, C 10 to C 44 , even number of hydrocarbons, 200 parts per million (ppm) of n-decane, n-tetradecane, and n-tricosane and all other components were 100 ppm in hexane) were analyzed by GC with a split/splitless inlet and flame ionization detector.
  • the peak area for all peaks eluting between methylene chloride and C 44 H 90 was determined using a chromatographic data system.
  • the peak areas for additives, such as Irgafos 168, oxidized I-168 and Irganox 1076 were excluded using the settings in the chromatographic data system.
  • the parts per million of oligomers was calculated from the total peak area of the oligomer peaks in the sample and the peak area of the 100 ppm n-eicosane (C 20 H 42 ) peak in the calibration standard using an external standard calibration procedure.
  • the samples were prepared by adding approx. 130 mg of sample to 3.25g of 50/50 by weight Tetrachlorethane-d2/Perchloroethylene with 0.001 M Cr (AcAc) 3, and 100 ppm antioxidant (Irganox168) , in a NORELL 1001-7, 10 mm, NMR tube.
  • the samples were purged by bubbling N 2 through the solvent, via a pipette inserted into the tube, for approximately five minutes to prevent oxidation.
  • the tube was next capped, sealed with TEFLON tape, and then soaked at room temperature overnight to facilitate sample dissolution.
  • the samples were kept in a N 2 purge box during storage, before, and after preparation, to minimize exposure to O 2 .
  • the samples were heated, and vortexed at 110°C, to ensure homogeneity.
  • Moles of respective unsaturation were calculated by dividing the area under the unsaturation resonance by the number of protons contributing to that resonance.
  • Moles of carbons in the polymers were calculated by dividing the area under the peaks for polymer chains (i.e., CH, CH 2 , and CH 3 in the polymers) by two. The amount of total unsaturation was then expressed as a relative ratio of moles of total unsaturation to the moles of carbons in the polymers, with expression of the number of unsaturation per 1000 Carbon.
  • DMS Dynamic mechanical spectroscopy
  • the rheology of the elastomers was analyzed by DMS using an Advanced Rheometric Expansion System (ARES) equipped with 25 mm stainless steel parallel plates. Constant temperature dynamic frequency sweeps in the range of 0.1 to 500 rad/s were performed under nitrogen at 190 °C. Samples approximately 25.4 mm in diameter were cut from compression molded parts. The sample was placed on the lower plate and allowed to melt for 5 min. The plates were then closed to a gap of 2.0 mm and the sample trimmed to 25 mm in diameter. The samples were allowed to equilibrate at 190 °C for the elastomers for 5 min before starting the test. The complex viscosity was measured at a constant strain amplitude of 10%. The complex viscosity measured at 0.1 rad/s is reported as V 0.1 and the complex viscosity measured at 100 rad/s is reported as V 100 .
  • V 0.1 The complex viscosity measured at 0.1 rad/s
  • Transmittance was measure by Perkin Elmer Lambda 950 equipped with integrating spheres on the sample with a thickness of 0.5 mm which is prepared at compression molding process:
  • Thermoplastic film Preheating at 150°C for 5 min., followed by 3 min. at 150°Cunder 10 MPa and cooling to room temperature for 5 min. with 40°C cooling water circulated.
  • TEC Tert-Butylperoxy 2-ethylhexyl carbonate
  • TAEC Tert-Amylperoxy 2-ethylhexyl carbonate
  • TIC Triallyl isocyanurate
  • VMMS 3- (trimethoxysilyl) propylmethacrylate)
  • ENGAGE TM PV 8660 and ENGAGE TM PV 8669 are polyolefin elastomers available from The Dow Chemical Company, Midland, MI.
  • polystyrene foams utilized in the examples are provided in Tables 1A and 1B below.
  • the polyolefin elastomers of Tables 1A and 1B were prepared in a well-mixed, hydraulically full polymerization reactor that was operated at steady state conditions. All raw materials (ethylene monomer and 1-octene comonomer) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent, Isopar-E supplied by the ExxonMobil Chemical Company) were purified with molecular sieves before introduction into the reaction environment. Hydrogen was supplied pressurized as a high purity grade and is not further purified. Ethylene flowrate and reactor volume were selected to obtain the residence times specified in Table 2A. The catalysts and cocatalysts used are listed in Table 3.
  • the solvent, comonomer, hydrogen, catalysts, and cocatalysts were fed to the reactor according to the process conditions outlined in Tables 2A and 2B.
  • the catalyst flow was adjusted to achieve the desired ethylene conversion.
  • the reactor temperature was measured at or near the exit of the reactor.
  • the interpolymer was isolated and pelletized.
  • the BPP-A catalyst was prepared according to the following 3-step process:
  • This reaction was carried out in a nitrogen filled glove box.
  • a slurry of 1 (5.52 g, 19.3 mmol) , 2 (WO2022015369 A1) (1.65 g, 7.74 mmol) , and K 3 PO 4 (5.75 g, 27.1 mmol) in DMF (7 mL) was warmed to 75 °C and held at this temperature for 5 h with stirring. After this time the temperature was decreased to 70 °C and held at this temperature for 11 h with stirring. The mixture was removed from the glove box after cooling to room temperature.
  • Et 2 O (10 mL) was added to the reaction vial and the mixture was filtered through a 1: 1 (40 grams) basic alumina/SiO 2 gel plug.
  • the plug was further extracted with Et 2 O (3 x 30 mL) .
  • the combined Et 2 O extracts were transferred to a separatory funnel and washed with 4N NaOH (10 mL) , H 2 O (10 mL) , brine (10 mL) , 4N NaOH (10 mL) , H 2 O (10 mL) , and brine (10 mL) .
  • the Et 2 O layer was then dried over Na 2 SO 4 and filtered into a 250 mL RB flask to remove the Na 2 SO 4 .
  • the Et 2 O was removed on a rotovap to provide 3 (5.25 g, 7.39 mmol, yield: 96 %) as a colorless oil, which was used without further purification.
  • the yellow oil was rotovapped from isopropyl alcohol (IPA) (10 mL) , the oil was taken up in IPA (15 mL) , then placed into a rotovap bath and warmed to 55 °C while rotating. The solution was then taken out of the bath and rotated at room temperature, and a solid eventually precipitated. After being at room temperature for 1 hour, the solid was then collected by filtration. The solid was washed with IPA (2 x 3 mL) . IPA/MeOH (1: 1, 15 mL) was added to the solid (about 420 mg) in a 100 mL RB flask, then the flask was placed into a rotovap bath and warmed to 75 °Cwhile rotating.
  • IPA isopropyl alcohol
  • the suspension (not fully soluble) was then taken out of the bath and rotated at room temperature. After being at room temperature for 1 hour, the solid was then collected by filtration. The solid was washed with IPA (2 x 3 mL) . MeOH/Et 2 O (5: 1, 18 mL) was added to the solid (about 360 mg) in a 100 mL RB flask, then the flask was placed into a rotovap bath and warmed to 45 °C while rotating. The suspension (not fully soluble) was then taken out of the bath and kept at room temperature. After being at room temperature overnight, the solid was then collected by filtration.
  • MeMgBr (3 M in diethyl ether, 0.283 mL, 0.849 mmol) was added to a room temperature suspension of tetrachlorozirconium (0.0475 g, 0.204 mmol) and 5 (0.275 g, 0.200 mmol) in Et 2 O (10 mL) and toluene (2 mL) . The mixture was stirred for 4 h then additional MeMgBr (50 uL) was added, then the reaction was stirred overnight at room temperature. After this time the solvent was removed under reduced pressure. Pentane (10 mL) was added to the dark residue, then this was passed through a CELITE pad. The residue and pad were extracted with additional pentane (10 mL) .
  • BPP-A was found to result in high vinyl level on the chain-end in combination with low oligomer content in the polymers.
  • the POE resins of Table 1 were formed into the encapsulant film formulations of Tables 4-5 by using a Haake blender. Specifically, 35 g of pellets were melted in a Haake blender (RSI RS5000, Rheomix 600 mixer with CAM blades) with setting temperature of 100°C and a rotor speed of 10 RPM. After the pellets were fully melted, peroxide additives, silane coupling agents, and crosslinking coagents (see further details about these additives below) were added to form the polymer-additive blend formulations listed in Tables 4-5.
  • RSI RS5000 Haake blender
  • silane coupling agents silane coupling agents
  • crosslinking coagents see further details about these additives below
  • the rotor speed of the Haake bowl was further increased to 50 RPM for 5 minutes of blending, which eventually led to a plateaued torque of blending and melt temperature after mixing.
  • the plateaued mixing torque and final melt temperature were also recorded in the tables.
  • the polymer melt was cold pressed into a plaque with 4 mm thickness for other testing by using a compression molder at pressure of 20000 psi for 4 minutes at 20°C.
  • pellets of the polyolefin elastomers in Table 1 were mixed with the curing additives (peroxide, crosslinking coagent and silane coupling agent) in a fluoride HDPE bottle to form a cross-linkable polyolefin elastomer pellets.
  • the soaking process occurred via rolling the bottle and an imbibition for 5h at 50°C until all additives diffusing into pellets completely.
  • Table 4 above shows the curing efficiency of the PV encapsulant film formulations made from POE with comparable density, melting index, and oligomer level.
  • the high unsaturation POE clearly showed higher MDR torque change (MH-ML) , when comparing CE-A vs. IE-1 and CE-B vs. IE-2 and when comparing CE-C vs. IE-3 and CE-D vs. IE-4.
  • Table 5 above shows the curing efficiency with a different peroxide (dicumyl peroxide) , between two POE with comparable density, melting index, and oligomer level.
  • the high unsaturation POE clearly showed higher MDR torque change (MH-ML) .
  • Table 6 above shows improved curing properties of the POE with high vinyl and low oligomer content versus the comparative POEs.
  • the POE with higher vinyl content resulted in higher gel content at shorter lamination times, while also demonstrating equivalent or higher light transmittance, as demonstrated by IE-6 vs. CE-F and by IE-8 and IE-9 vs. CE-G and CE-H.
  • the comparison between CE-F (0.8 part TAIC) vs. IE9 (0.5 part TAIC) and CE-G/CE-H (0.8 part TAIC) vs. IE-10 (0.5 part TAIC) .
  • the POEs with high vinyl and low oligomer content versus the comparative POEs can reach the same or better level of crosslinking density from gel content measurements with less TAIC in the formulation.
  • the processability of the resins was further evaluated on Collin cast film line with a E30P single screw extruder (nominal cylinder diameter of 30 mm) .
  • the extruder was connected to a slot die, and to a cast film device to make film with thickness around 0.5 mm.
  • the polymer melt temperature was monitored by a thermocouple that was equipped to the exit of the extruder.
  • the resin pellets were initially fed and extruded at ⁇ 10 RPM extrusion speed, and gradually increasing RPM to let the final polymer melt temperature measured by the thermal couple stabilized at around 100 °C, and at the same time all the extruder zones were also confirmed to have lower temperature than 120°C.
  • a more processable resin will have less shear-heating (i.e. heat generation) at a particular the extrusion rate, and thus allows the polymers to be extruded at a higher RPM and higher extrusion rate without overheating the polymer formulation that can undergo pre-matured crosslinking at above 120 °C in the extruder.
  • the polymer temperature was constrained by the polymer melt temperature at the extruder exit not exceeding substantially from 100 °C.
  • the processing parameters including temperature of the polymer melt, temperatures at the surface of different zones, extrusion die pressure was recorded after equilibrating the extruder for 30 min.
  • the extrusion throughput was calculated based on the mass balance of fed pellets per hour.
  • the collected extrusion parameters and throughput rate are shown in Table 7.
  • the inventive resins, POE A and POE B can be extruded at higher throughput rate and higher RPM thereby indicating improved processability as compared to commercial products with comparable melting index, specifically, POE H and POE I. This is in addition to the improved crosslinking properties observed.
  • the LCB of the inventive resins leads to an increased extrusion rate and may also reduce neck-in.
  • POE G has high unsaturation but high oligomer content. Due to the higher oligomer content, it was observed that the POE G with higher vinyl content exhibited a worse curing performance, lower MH-ML, compared to the commercial product blend of POE H and POE I.

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Abstract

Des modes de réalisation concernent un élastomère polyoléfinique comprenant le produit réactionnel polymérisé d'un monomère éthylénique et d'au moins un comonomère alpha-oléfinique en C4-C12, l'élastomère polyoléfinique présentant : une densité de 0,860 à 0,900 g/cc ; un indice de fusion (I2) de 0,5 à 30 dg/min, I2 étant mesuré selon la norme ASTM D1238 (190 °C, 2,16 kg) ; un I10/I2 supérieur ou égal à 8, I10 étant mesuré selon la norme ASTM D1238 (190 °C, 10 kg) ; supérieur ou égal à 0,2 vinyle pour 1 000 carbones ; le pourcentage de vinyles dans l'insaturation totale étant supérieur ou égal à 50 % ; et un niveau d'oligomère inférieur à 5 000 ppm. Des modes de réalisation supplémentaires concernent le procédé de fabrication de l'élastomère polyoléfinique. D'autres modes de réalisation concernent des formulations d'élastomères polyoléfiniques réticulables et des élastomères polyoléfiniques réticulés et des articles produits à partir de celles-ci.
PCT/CN2024/074294 2024-01-26 2024-01-26 Élastomères polyoléfiniques (poe) pour des encapsulants photovoltaïques et leurs procédés de fabrication Pending WO2025156277A1 (fr)

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PCT/CN2025/075205 WO2025157309A1 (fr) 2024-01-26 2025-01-26 Conducteurs revêtus comprenant des compositions d'élastomère polyoléfinique réticulé
PCT/CN2025/075191 WO2025157305A1 (fr) 2024-01-26 2025-01-26 Élastomères de polyoléfine greffés par alcoxysilane et articles fabriqués à partir de ceux-ci
PCT/CN2025/075199 WO2025157307A1 (fr) 2024-01-26 2025-01-26 Élastomère de polyoléfine présentant une aptitude au traitement et un temps de durcissement améliorés
PCT/CN2025/075221 WO2025157311A1 (fr) 2024-01-26 2025-01-26 Compositions comprenant un interpolymère d'éthylène/alpha-oléfine, un polymère à base d'oléfine et un agent de réticulation, ainsi qu'articles fabriqués à partir de celles-ci
PCT/CN2025/075183 WO2025157303A1 (fr) 2024-01-26 2025-01-26 Compositions expansibles comprenant des élastomères de polyoléfine (poe)
PCT/CN2025/075187 WO2025157304A1 (fr) 2024-01-26 2025-01-26 Élastomères de polyoléfine (epo) et leurs procédés de fabrication

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PCT/CN2025/075205 Pending WO2025157309A1 (fr) 2024-01-26 2025-01-26 Conducteurs revêtus comprenant des compositions d'élastomère polyoléfinique réticulé
PCT/CN2025/075187 Pending WO2025157304A1 (fr) 2024-01-26 2025-01-26 Élastomères de polyoléfine (epo) et leurs procédés de fabrication
PCT/CN2025/075191 Pending WO2025157305A1 (fr) 2024-01-26 2025-01-26 Élastomères de polyoléfine greffés par alcoxysilane et articles fabriqués à partir de ceux-ci
PCT/CN2025/075199 Pending WO2025157307A1 (fr) 2024-01-26 2025-01-26 Élastomère de polyoléfine présentant une aptitude au traitement et un temps de durcissement améliorés
PCT/CN2025/075221 Pending WO2025157311A1 (fr) 2024-01-26 2025-01-26 Compositions comprenant un interpolymère d'éthylène/alpha-oléfine, un polymère à base d'oléfine et un agent de réticulation, ainsi qu'articles fabriqués à partir de celles-ci
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PCT/CN2025/075191 Pending WO2025157305A1 (fr) 2024-01-26 2025-01-26 Élastomères de polyoléfine greffés par alcoxysilane et articles fabriqués à partir de ceux-ci
PCT/CN2025/075199 Pending WO2025157307A1 (fr) 2024-01-26 2025-01-26 Élastomère de polyoléfine présentant une aptitude au traitement et un temps de durcissement améliorés
PCT/CN2025/075221 Pending WO2025157311A1 (fr) 2024-01-26 2025-01-26 Compositions comprenant un interpolymère d'éthylène/alpha-oléfine, un polymère à base d'oléfine et un agent de réticulation, ainsi qu'articles fabriqués à partir de celles-ci
PCT/CN2025/075183 Pending WO2025157303A1 (fr) 2024-01-26 2025-01-26 Compositions expansibles comprenant des élastomères de polyoléfine (poe)

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