WO2016198405A1 - Compositions polymères et traitements associés - Google Patents

Compositions polymères et traitements associés Download PDF

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Publication number
WO2016198405A1
WO2016198405A1 PCT/EP2016/062906 EP2016062906W WO2016198405A1 WO 2016198405 A1 WO2016198405 A1 WO 2016198405A1 EP 2016062906 W EP2016062906 W EP 2016062906W WO 2016198405 A1 WO2016198405 A1 WO 2016198405A1
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Prior art keywords
polymer
solvent
composition
crystallization temperature
less
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PCT/EP2016/062906
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English (en)
Inventor
Theodorus Tervoort
Paul Smith
Raphael Schaller
Kirrill FELDMAN
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Eidgenössische Technische Hochschule Zürich
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Publication of WO2016198405A1 publication Critical patent/WO2016198405A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the present invention relates, inter alia, to polymer compositions, to processing the compositions, and to products made by processing the compositions.
  • Ultra-high molecular weight polyethylene UHMWPE
  • UHMWPE ultra-high molecular weight polyethylene
  • composition comprising a polymer and a solvent for the polymer, wherein the solvent comprises a vegetable oil.
  • composition comprising a polymer and a solvent for the polymer, wherein the solvent is a relatively poor solvent for the polymer.
  • the composition comprises a high molecular weight polymer, in a relatively high polymer concentration, despite use of a relatively poor solvent.
  • a process comprising extracting, from a composition comprising a polymer and a solvent for the polymer, at least part of said solvent with a supercritical fluid.
  • FIG. 1 represents thermogravimetric analysis (TGA) curves of various solvents.
  • compositions comprising a polymer and a solvent, wherein the solvent is a relatively poor solvent for the polymer.
  • a parameter for determining the solubility quality of a solvent for a polymer is the crystallization temperature depression of the polymer that the solvent causes. This can be determined by comparing the peak crystallization temperature of the pure polymer with the peak crystallization temperature of the polymer in the solvent, as observed in differential scanning calorimetry (DSC) measurements [by heating from room temperature (25 °C) to above the crystalline melting temperature of the polymer (at a rate of 10°C/min), and then determining the peak crystallization temperature by subsequent cooling (also at a rate of 10°C/min)].
  • DSC differential scanning calorimetry
  • the solvent causes a crystallization temperature depression of the polymer of less than 10°C, e.g. less than 7°C or less than 5°C. In an embodiment, the crystallization temperature depression is more than 1°C, e.g. more than 3 °C.
  • the polymer may exhibit high chain swell. This, in turn, may result in high composition viscosity and associated processing difficulties and/or may force use of relatively low polymer concentrations. If the
  • the desired crystallization temperature depression is very low, the solvent may be too poor and not provide enough solubility or polymer disentanglement for adequate processing.
  • the desired crystallization temperature depression may be obtained by using a single solvent causing the desired crystallization temperature depression, but may also be obtained e.g. by combining a solvent of higher crystallization temperature depression with a solvent of lower crystallization temperature depression or even with a non-solvent.
  • the above crystallization depression numbers apply at least to the polymer that is present in the composition in the highest concentration.
  • the solvent is selected from the group of solvents that, when compounded with polyethylene having a density of 0.93 g/cm and an elongational stress (F150/10), according to ISO 11542-2, of 0.51 MPa at a ratio of 80 wt% solvent and 20 wt%
  • polyethylene relative to the total amount of solvent and polyethylene, causes a reduction in crystallization temperature of the polyethylene in the range of 1-7°C.
  • a solvent comprising a conventional solvent (e.g., decalin) and at least one other component that has lower crystallization temperature depression (or even is a non-solvent).
  • a conventional solvent e.g., decalin
  • the composition comprises at least 80wt , relative to the total weight of solvent, of conventional solvent. In an embodiment, the composition comprises less than 95wt , relative to the total weight of solvent, of
  • compositions comprising a polymer and a solvent, wherein the solvent includes a vegetable oil.
  • Vegetable oils are generally non-hazardous and/or renewable and/or edible and/or relatively cheap.
  • Using one or more vegetable oils as (part of) the solvent may help in decreasing or eliminating hazardous, non-renewable, and/or costly components in the solvent. Examples are, e.g., olive oil, peanut oil, coconut oil, canola
  • the solvent includes peanut oil.
  • at least 50 wt of the solvent is comprised of a vegetable oil, e.g. at least 60 wt%, at least 80 wt%, at least 95 wt%, or 100 wt%.
  • the composition includes an oil, e.g. a vegetable oil, comprising saturated fat, and/or mono-unsaturated fat, and/or poly-unsaturated fat.
  • the composition comprises an oil having, relative to the total amount of oil, between 5-30 wt saturated components, between 20-80 wt (e.g. between 50-80 wt ) mono-unsaturated components, and between 5-65 wt (e.g. 5-35 wt ) poly-unsaturated components.
  • the solvent has good thermal stability.
  • the solvent exhibits less than 5 % weight loss in a thermo gravimetric (TGA) measurement from 25°C to 225°C (heating rate 2°C/min; nitrogen atmosphere).
  • TGA thermo gravimetric
  • good thermal stability may allow processing (e.g. compounding of polymer and solvent) at higher temperatures, which may assist in faster and/or more homogeneous processing.
  • the solvent is not a solid at 25 °C. In an embodiment, the solvent is a liquid at 25 °C. In an embodiment, the solvent is a paste at 25 °C. Using a liquid or paste may help in preventing compositions being brittle, which -in some embodiments- can have processing advantages (e.g., may avoid higher processing temperatures and/or may facilitate shaping/stretching the compositions).
  • the composition comprises a semicrystalline polymer.
  • the composition comprises a polymer selected from the group of polyethylene, polypropylene, polystyrene, polybutene-1, and poly(transisoprene).
  • the composition comprises a polyolefin.
  • the composition comprises a polyethylene.
  • the composition comprises a UHMW (ultra-high molecular weight)
  • the polymer comprises co-monomer.
  • the composition comprises a polymer having up to 10 wt , relative to the total weight of the polymer, of co- monomer, e.g. up to 5 wt .
  • the polymer has at least 0.5 wt co- monomer.
  • the co-monomer is an alpha-olefin co-monomer, e.g. an alpha olefin co-monomer having up to 20 carbon atoms, e.g. up to 10 carbon atoms or up to 5 carbon atoms.
  • the co-monomer is selected from the group of propylene, 1- butene, 1-pentene, 4-methyl-pentene, 1-hexene, and 1-octene.
  • the composition comprises a polymer having a weight average molecular weight of at least 500 kg/mol, e.g. at least 1000 kg/mol, at least 2000 kg/mol, or at least 4000 kg/mol.
  • the polymer has a weight average molecular weight of less than 15000 kg/mol, e.g. less than 12000 kg/mol, less than 9000 kg/mol or less than 7000 kg/mol.
  • the weight average molecular weight is in the range of 3000-8000 kg/mol.
  • the weight average molecular weight is in the range of 3000-5000 kg/mol.
  • the composition comprises a polyolefin having an elongational stress F(150/10) of at least 0.15 MPa, e.g. at least 0.2 MPa. In an embodiment, the elongational stress F(150/10) is less than 0.6 MPa.
  • the composition comprises, relative to the total weight of polymer and solvent, 5 or more wt of polymer, e.g. at least 10 wt of polymer, at least 15 wt or at least 20 wt . In an embodiment, the composition comprises, relative to the total weight of polymer and solvent, less than 75 wt of polymer, e.g. less than 60 wt , less than 50 wt , less than 40 wt , or less than 35 wt . In an embodiment, the composition comprises 15-25 wt polymer.
  • the composition comprises one or more additives, e.g. antioxidants, nucleating agents, clarifying agents, colorants, blowing agents, foaming agents, or fillers.
  • the composition comprises antioxidants.
  • At least 50 wt relative to the total weight of the composition, consists of polymer and solvent, e.g. at least 70 wt , at least 85 wt , at least 95 wt , or at least 98 wt .
  • compositions consist, or consist essentially, of the polymer, the solvent, and -optionally- additives.
  • the composition has a melt flow rate "MFR" (IS01133, 10 kg, 180 °C) of at least 10 g/min, e.g. at least 15 g/min or at least 20 g/min. In an embodiment, the composition has a melt flow rate of less than 50 g/min.
  • MFR melt flow rate
  • the compositions are processed into a product, e.g. by extruding the compositions, or by injection molding, blow molding, calendaring, compression molding, transfer molding, spinning, and the like.
  • the solvent and polymer, and optionally other components are mixed during said processing to form the composition.
  • the composition is already formed prior to said processing.
  • the process is a gel -processing process.
  • the compositions are processed into products such as fibers, films, foams, or membranes.
  • the products e.g. fibers or films, are subsequently drawn to enhance the mechanical properties.
  • the products are drawn in one direction.
  • the products are drawn in more than one, e.g. in two, directions.
  • the products are drawn to a draw ratio of at least 30, e.g. at least 50, at least 60, at least 70, or at least 80. In an embodiment, the draw ratio is less than 150, e.g. less than 120 or less than 100.
  • the solvent is at least partly removed from the product, e.g. by extraction. In an embodiment, the extraction comprises washing the product in isopropanol. In an embodiment, the extraction comprises exposing the product to a supercritical fluid, e.g. a supercritical fluid comprising, or consisting essentially of, supercritical carbon dioxide.
  • a supercritical fluid such as carbon dioxide may reduce the amount of hazardous, flammable, and/or toxic chemicals used.
  • the solvent is at least partly removed during the above-mentioned drawing. In an embodiment, the solvent is at least partly removed prior to the above-mentioned drawing. In an embodiment, the solvent is at least partly removed past the above-mentioned drawing. In an embodiment, not all of the solvent is removed from the product. E.g., in embodiments where removing all solvent is not cost-effective and/or in embodiments where it is
  • the product comprises more than 0.05 wt , relative to the total weight of polymer and solvent, solvent. For instance more than 0.1 wt or more than 0.25 wt . In an embodiment, the product comprises less than 15 wt , relative to the total weight of polymer and solvent, solvent. For instance less than 10 wt , less than 5 wt , less than 1.5 wt%, less than 0.75 wt , less than 0.4 wt , or less than 0.2 wt . In an embodiment, the product, e.g. fiber or film, has after drawing a modulus of at least 40 GPa, e.g.
  • the modulus is less than 250 GPa, e.g. less than 200 GPa.
  • the product, e.g. fiber or film has a strength after drawing of at least 2.1 GPa, e.g. at least 2.5 GPa, at least 2.8 GPa, at least 3.2 GPa, or at least 3.4 GPa.
  • the strength is less than 5.0 GPa, e.g. less than 4.5 GPa, less than 4.0 GPa, or less than 3.5 GPa.
  • articles comprising, or consisting of, the products, e.g., an anti-ballistic article (bulletproof vests, bulletproof helmets, bulletproof panels, etc.), a fishing line, a fishing net, a sports article (e.g. a tennis racket), a rope, a balloon, a surgical suture, a dental floss, a porous membrane, a battery separator, or a sail.
  • an anti-ballistic article bulletproof vests, bulletproof helmets, bulletproof panels, etc.
  • a fishing line e.g. a fishing net
  • a sports article e.g. a tennis racket
  • a rope e.g. a tennis racket
  • a balloon e.g. a surgical suture
  • dental floss e.g., a dental floss
  • porous membrane e.g., a battery separator, or a sail.
  • granulate comprising a composition according to the present invention. This may be obtained, e.g
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has an elongational stress F(150/10) of at least 0.15MPa
  • the polymer is a polyolefin
  • the composition has a crystallization temperature that is less than 10 °C lower, e.g. less than 7 °C lower, than the crystallization temperature of the polymer.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has an elongational stress F(150/10) of at least 0.15 MPa
  • the polymer is a polyolefin
  • the solvent comprises a vegetable oil.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has an elongational stress F(150/10) of at least 0.15 MPa
  • the polymer is a polyolefin
  • the composition has a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polymer
  • a composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has an elongational stress F(150/10) of at least 0.15 MPa
  • the polymer is a polyolefin
  • the composition has a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polymer
  • the solvent is selected from the group of solvents that shows less than 5 wt weight decrease in a TGA measurement from 25 °C to 250 °C.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the composition has a crystallization temperature that is less than 10 °C lower, e.g. less than 7 °C lower, than the crystallization temperature of the polymer.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the solvent comprises a vegetable oil.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the composition has a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polymer
  • a composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the composition has a crystallization temperature that is less than IOC lower than the crystallization temperature of the polymer
  • the solvent is selected from the group of solvents that shows less than 5wt weight decrease in a TGA measurement from 25 °C to 250 °C.
  • composition according to any one of embodiments 1-15 wherein the polymer comprises up to 5 wt , relative to the total weight of the polymer, of co-monomer. 18. The composition according to any one of embodiments 1-17, wherein the polymer comprises an alpha-olefin co-monomer having up to 20 carbon atoms.
  • the polymer comprises an alpha-olefin co-monomer having up to 5 carbon atoms.
  • composition according to any one of embodiments 1-20, wherein the composition comprises, relative to the total weight of polymer and solvent, at least 10 wt polymer.
  • composition according to any one of embodiments 1-29 wherein the solvent comprises a poly-unsaturated vegetable oil.
  • the solvent has a density that is less than 10 % different from the density of the polymer.
  • composition according to any one of embodiments 1-33, wherein the composition has an MFR in the range of 10-35 g/lOmin.
  • composition comprising polyethylene and a solvent for the polyethylene, wherein:
  • the polyethylene has a weight average molecular weight in the range of 2000-15000 kg/mol;
  • the solvent comprises a vegetable oil
  • the composition comprises, relative to the total weight of the polyethylene and the solvent, 10-30 wt polyethylene.
  • composition of embodiment 36, wherein the polyethylene comprises up to 5 wt , relative to the total weight of polyethylene, of co-monomer.
  • a composition comprising a plurality of polymers and a solvent for the plurality of polymers, the plurality of polymers including a polymer having a molecular weight of at least 500 kg/mol, and the composition having a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polymer having a molecular weight of at least 500 kg/mol.
  • composition of embodiment 41, wherein the solvent includes a vegetable oil includes a vegetable oil.
  • composition comprising a polymer and a solvent, wherein
  • the polymer is a polyolefin
  • the polymer has an elongational stress (F150/10) of at least 0.15MPa
  • the polymer is present in an amount of at least 10 wt , relative to the total amount of polymer and solvent, and
  • the solvent is selected from the group of solvents that, when compounded with polyethylene having a density of 0.93 g/cm and an elongational stress (F150/10) of 0.51MPa at a ratio of 80 wt solvent and 20wt polyethylene, relative to the total amount of solvent and polyethylene, causes a reduction in crystallization temperature of the polyethylene in the range of 1-7 °C.
  • composition comprising a polymer and a solvent, wherein
  • the polymer has a weight average molecular weight of at least 1000 kg/mol
  • the polymer is present in an amount of at least 10 wt , relative to the total amount of polymer and solvent, and
  • the solvent is selected from the group of solvents that, when compounded with polyethylene having a density of 0.93 g/cm and an elongational stress F(150/10) of 0.51MPa at a ratio of 80wt solvent and 20wt polyethylene, relative to the total amount of solvent and polyethylene, causes a reduction in crystallization temperature of the polyethylene in the range of 1-7 °C.
  • a composition comprising a polymer and a solvent for the polymer, wherein - the polymer has an elongational stress F(150/10) of at least 0.15MPa,
  • the polymer is a polyolefin
  • the solvent comprises decalin and at least one other component.
  • composition of embodiment 46, wherein the solvent comprises, relative to the total weight of the solvent, at least 80 wt decalin.
  • composition according to any one of embodiments 46-48, wherein the at least one other component includes mineral oil or paraffin oil.
  • composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the solvent comprises decalin and at least one other component.
  • composition of embodiment 53, wherein the solvent comprises, relative to the total weight of the solvent, at least 80 wt decalin.
  • composition according to any one of embodiments 53-54 wherein the solvent comprises, relative to the total weight of the solvent, less than 95 wt decalin.
  • the at least one other component includes a non-solvent for the polymer.
  • composition according to any one of embodiments 46-65 wherein the composition comprises, relative to the total weight of polymer and solvent, at least 10 wt polymer.
  • composition according to any one of embodiments 46-66 wherein the composition comprises, relative to the total weight of polymer and solvent, at most 60 wt polymer.
  • composition according to any one of embodiments 46-65, wherein the composition comprises, relative to the total weight of polymer and solvent, 15-35 wt polymer.
  • composition according to any one of embodiments 46-68 wherein the composition consists essentially of said polymer and solvent. 70. The composition according to any one of embodiments 46-68, wherein the composition consists of said polymer, said solvent, and one or more additives.
  • a process comprising processing the composition according to any one of embodiments 1-70 to form a shaped product.
  • a foam, foil, tape, sheet, plaque, tube, container, felt, or membrane obtained with the process according to any one of embodiments 71-74.
  • the fiber of embodiment 86 the fiber having a tensile modulus of at least 100 GPa.
  • the fiber of embodiment 87 the fiber having a tensile modulus of 130-180 GPa.
  • a polyolefin product comprising vegetable oil, the oil being present in an amount of less than 5 wt , relative to the total amount of polyolefin and oil.
  • An article comprising the product according to any one of embodiments 85-96, the article being an anti-ballistic article, a rope, a fishing article, a panel, a balloon, a sports article, a surgical suture, a dental floss, a porous membrane, a battery separator, or a sail.
  • Granulate comprising the composition according to any one of embodiments 1-45.
  • a composition comprising a polyolefin, the polyolefin comprising co-monomer, and a solvent for the polyolefin, wherein
  • the polymer has an elongational stress F(150/10) of at least 0.15 MPa
  • the composition has a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polyolefin.
  • composition comprising a polyolefin, the polyolefin comprising co-monomer, and a solvent for the polyolefin, wherein
  • the polymer has a weight average molecular weight of at least 500 kg/mol
  • the composition has a crystallization temperature that is less than 10 °C lower than the crystallization temperature of the polyolefin.
  • a process comprising gel-processing a polyethylene having a weight average molecular weight of at least 500kg/mol, wherein the polyethylene comprises co-monomer.
  • a process comprising removing solvent from a composition comprising a polymer and a solvent for said polymer, wherein said removing includes exposing the composition to a supercritical fluid.
  • a process comprising:
  • composition to form a shaped product, the composition comprising a polymer and a solvent for the polymer, wherein
  • the polymer has a weight average molecular weight of at least 8000 kg/mol
  • composition comprises, relative to the total weight of polymer and solvent, at least 10 wt polymer;
  • PE-1 is an ultra-high molecular weight polyethylene with a density of 0.93 g/cm , measured according to ISO 1183 test method A, and an elongational stress F(150/10) of 0.51 MPa, measured according to ISO 11542-2. It is commercially sold by Ticona under the name GUR4150.
  • PE-2 referred to in the examples is an ultra-high molecular weight polyethylene, comprising co-monomer, with a density of 0.925 g/cm , measured according to ISO 1183 test method A, and an elongational stress F(150/10) of 0.2 MPa, measured according to
  • Polymer powder, antioxidant, and solvent were added to a round-bottom flask.
  • the antioxidants used were Irganox 1010 and Irgafos 1068, both from Ciba AG, Switzerland, each in an amount of 0.5 wt relative to the total weight of polymer.
  • the amounts of polymer and solvent, except where expressly indicated otherwise, are expressed in weight relative to the total amount of polymer + solvent.
  • the flask was heated to 90 °C to ensure dissolution of the antioxidant in the solvent; the resulting slurry was kept under continuous mixing with a magnetic stirrer.
  • Tensile measurements were conducted with an Instron 5864 static mechanical tester, fitted with 100 N load cell and equipped with pneumatic clamps. The crosshead speed was set to 20 mm/min. All tests on the drawn samples were performed at room temperature (22 - 24 °C). The samples had a gauge length of 70 mm; the cross-sectional area was calculated from sample length and sample weight, assuming a density of 1 g/cm . Unless indicated otherwise, all reported values for the modulus, tensile strength, and elongation at break refer to an average of at least three measurements.
  • melt flow rate (MFR) of PE-1 compositions was 20:80 (wt:wt) was measured with a melt-flow indexer (MeltFlow LT, Haake, Germany) according to ISOl 133, using a weight of 10 kg at a temperature of 180 °C. All reported values refer to an average of 7 measurements, atlO minutes collection time.
  • Differential scanning calorimetry was performed using a DSC 822e from Mettler Toledo, Switzerland, and calibrated with Indium. DSC thermograms were recorded under nitrogen at heating and cooling rates of 10 °C/min. Samples were heated from 25 °C to 180 °C and then cooled to 25 °C ("first cooling curve"). The sample weight was about 10 mg. Reported crystallization temperature values are the peak crystallization temperatures in the first cooling scans.
  • TGA Thermo gravimetric analysis
  • melt flow rates of various PE-l/solvent compositions were determined. See Table 2.
  • Table 2 Melt-flow rates (MFR).

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des compositions comprenant un polymère et un solvant, et qui peuvent être utilisées, par exemple, pour le traitement de gels. Un exemple est une composition comprenant un polymère de polyéthylène et une huile végétale. Le solvant peut être un solvant assez pauvre pour le polymère. Le solvant peut être extrait de la composition en utilisant un fluide supercritique.
PCT/EP2016/062906 2015-06-08 2016-06-07 Compositions polymères et traitements associés WO2016198405A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10567084B2 (en) 2017-12-18 2020-02-18 Honeywell International Inc. Thermal interface structure for optical transceiver modules

Citations (7)

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US4422993A (en) 1979-06-27 1983-12-27 Stamicarbon B.V. Process for the preparation of filaments of high tensile strength and modulus
WO1996026059A1 (fr) * 1995-02-22 1996-08-29 Novartis Ag Procede de degagement, d'extraction et de nettoyage d'articles polymeres a l'aide d'un fluide supercritique
GB2311992A (en) * 1996-04-10 1997-10-15 Bespak Plc A method of cleaning or purifying elastomers and elastomeric articles which are intended for medical or pharmaceutical uses
DE29923414U1 (de) * 1999-11-05 2000-11-16 Hiendl Gmbh & Co Kg H Dichtungsmaterial, insbesondere Fugendichtungsmaterial
WO2008116613A1 (fr) * 2007-03-27 2008-10-02 Dsm Ip Assets B.V. Méthode permettant d'éliminer un solvant résiduel d'un filament filé par gel, filament, fil multifilament et produits comprenant ledit filament
KR20110033388A (ko) * 2009-09-25 2011-03-31 그린텍이십일 주식회사 준연속식 순환방식의 초임계 이산화탄소 유체 추출 공정에 의한 저지방 유탕면 제조장치 및 제조방법
US20150119545A1 (en) * 2013-10-30 2015-04-30 Sk Innovation Co.,Ltd. Method of fabricating thermal conductive polymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4422993A (en) 1979-06-27 1983-12-27 Stamicarbon B.V. Process for the preparation of filaments of high tensile strength and modulus
WO1996026059A1 (fr) * 1995-02-22 1996-08-29 Novartis Ag Procede de degagement, d'extraction et de nettoyage d'articles polymeres a l'aide d'un fluide supercritique
GB2311992A (en) * 1996-04-10 1997-10-15 Bespak Plc A method of cleaning or purifying elastomers and elastomeric articles which are intended for medical or pharmaceutical uses
DE29923414U1 (de) * 1999-11-05 2000-11-16 Hiendl Gmbh & Co Kg H Dichtungsmaterial, insbesondere Fugendichtungsmaterial
WO2008116613A1 (fr) * 2007-03-27 2008-10-02 Dsm Ip Assets B.V. Méthode permettant d'éliminer un solvant résiduel d'un filament filé par gel, filament, fil multifilament et produits comprenant ledit filament
KR20110033388A (ko) * 2009-09-25 2011-03-31 그린텍이십일 주식회사 준연속식 순환방식의 초임계 이산화탄소 유체 추출 공정에 의한 저지방 유탕면 제조장치 및 제조방법
US20150119545A1 (en) * 2013-10-30 2015-04-30 Sk Innovation Co.,Ltd. Method of fabricating thermal conductive polymer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10567084B2 (en) 2017-12-18 2020-02-18 Honeywell International Inc. Thermal interface structure for optical transceiver modules

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