WO2019165359A1 - Compositions de polyphosphonates et de nanotubes de carbone - Google Patents

Compositions de polyphosphonates et de nanotubes de carbone Download PDF

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WO2019165359A1
WO2019165359A1 PCT/US2019/019396 US2019019396W WO2019165359A1 WO 2019165359 A1 WO2019165359 A1 WO 2019165359A1 US 2019019396 W US2019019396 W US 2019019396W WO 2019165359 A1 WO2019165359 A1 WO 2019165359A1
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cnt
phosphonate
composition
bis
carbon nanotubes
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PCT/US2019/019396
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English (en)
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Xiudong Sun
Yan Li
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Frx Polymers, Inc.
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Publication of WO2019165359A1 publication Critical patent/WO2019165359A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present disclosure is directed to mixtures of polyphosphonates with carbon nanotubes (CNTs) and blends of polycarbonate and polyphosphonate with CNTs, and methods of manufacturing and using the same.
  • CNTs carbon nanotubes
  • the present disclosure provides compositions and methods of manufacturing a mixture of polyphosphonates with CNTs and blends of polycarbonate and polyphosphonate with CNTs.
  • the polymeric composition can comprise one or more polycarbonate, one or more polyphosphonate, and CNTs.
  • Some embodiments provide a composition comprising a phosphor containing flame retardant, and carbon nanotubes (CNT).
  • CNT carbon nanotubes
  • Some embodiments further comprise a polycarbonate (PC).
  • PC polycarbonate
  • the phosphor containing flame retardant is a phosphonate compound.
  • the carbon nanotubes are single wall carbon nanotubes, multi wall carbon nanotubes, or a combination thereof.
  • the loading of CNT is X).lwt% and the loading of the phosphor containing flame retardant is such that P content is > 3wt%.
  • the loading of CNT is X).2wt% and the loading of the phosphor containing flame retardant is such that P content is >2wt%.
  • the CNT are added as a blend of polycarbonate and
  • the CNT are added as a blend of a phosphonate compound and CNT.
  • the phosphonate compound is an oligomer, homopolymer, copolymer, non-linear polymer, or any combination thereof.
  • the phosphonate compound is selected from the group consisting of polyphosphonate, random polyphosphonate-co-carbonate, polyphosphonate-co-ester, oligophosphonate, co-oligo(phosphonate ester), co- oligo(phosphonate carbonate), or any combination thereof.
  • Some embodiments further comprise a reinforcement material selected from the group consisting of continuous, woven, or chopped fibers of glass, carbon, silicon carbide, organic fibers, and combinations thereof
  • Some embodiments further comprise at least one dispersing agent.
  • Some embodiments provide a polymer sheet made from a polymeric composition comprising polycarbonate (PC), phosphor containing flame retardant, and carbon nanotubes (CNT) where wt%P - 3.7 * wt%CNT > 3.5 and wt%P - 8.2 * wt%CNT +1.6 * Thickness (mm) > 4.3.
  • PC polycarbonate
  • CNT carbon nanotubes
  • the phosphor containing flame retardant is a phosphonate compound.
  • Some embodiments provide an article made from a composition of any of those described above and herein.
  • Some embodiments provide a polymer sheet made from a composition of any of those described above and herein, where wt%P - 3.7 * wt%CNT > 3.5 and wt%P - 8.2 * wt%CNT +1.6 * Thickness (mm) > 4.3.
  • the article is a polymer sheet.
  • FIG. 1 shows a picture of flammability testing set-up.
  • FIG. 2A shows a picture of control sample 1 without carbon nanotube.
  • FIG. 2B shows a picture of a front view of a polymeric composition with 0.53% carbon nanotube.
  • FIG. 2C shows a picture of a back view of a polymeric composition with 0.53% carbon nanotube.
  • FIG. 3 A shows a picture of a front view the control sample Ultem 1010.
  • FIG. 3 A shows a picture of a back view the control sample Ultem 1010.
  • thermoplastic polymers by nature, will melt and flow under heat.
  • FR Flammability Requirements
  • such melting behavior could deem the material unsatisfactory.
  • FAR 25.853 the flammability test for aircraft materials, dripping and melting of materials during the heat release test could fail the test. Therefore, it is important to develop a thermoplastic composition where melting/dripping under heat is effectively suppressed. Once solution is to develop polymer nanocomposite.
  • a common challenge in polymer nanocomposite preparation is establishing a good nanoparticle dispersion in the host polymer matrix. Good dispersion of the fillers is important to realize the exceptional properties. However, this is a difficult task because of the high specific surface area and strong intermolecular forces associated with these nanoparticles. Moreover, since the predominant nanoparticles are inorganic and the surfaces are usually hydrophilic, they need to be modified/functionalized for improving interaction and compatibility with the typically hydrophobic polymers.
  • substantially no means that the subsequently described event may occur at most about less than 10 % of the time or the subsequently described component may be at most about less than 10 % of the total composition, in some embodiments, and in others, at most about less than 5 %, and in still others at most about less than 1 %.
  • alkyl refers to a branched or unbranched hydrocarbon or group of 1 to 20 carbon atoms, such as but not limited to methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • Cycloalkyl or “cycloalkyl groups” are branched or unbranched hydrocarbons in which all or some of the carbons are arranged in a ring such as but not limited to cyclopentyl, cyclohexyl, methylcyclohexyl and the like.
  • the term “lower alkyl” includes an alkyl group of 1 to 10 carbon atoms.
  • aryl refers to monovalent aromatic hydrocarbon radicals or groups consisting of one or more fused rings in which at least one ring is aromatic in nature.
  • Aryls may include but are not limited to phenyl, napthyl, biphenyl ring systems and the like.
  • the aryl group may be unsubstituted or substituted with a variety of substituents including but not limited to alkyl, alkenyl, halide, benzylic, alkyl or aromatic ether, nitro, cyano and the like and combinations thereof.
  • Substituent refers to a molecular group that replaces a hydrogen in a compound and may include but are not limited to trifluoromethyl, nitro, cyano, CI -20 alkyl, aromatic or aryl, halide (F, CI, Br, I), Cl-20 alkyl ether, Cl-20 alkyl ester, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxy, alkoxy, amino, alkylamino (-NHR'), dialkylamino (-NR'R”) or other groups which do not interfere with the formation of the intended product.
  • an "arylol” or an “arylol group” is an aryl group with a hydroxy-, OH substituent on the aryl ring.
  • Non-limiting examples of an arylol are phenol, naphthol, and the like.
  • a wide variety of arlyols may be used in the embodiments of the invention and are commercially available.
  • alkanol or “alkanol group” refers to a compound including an alkyl of 1 to 20 carbon atoms or more having at least one hydroxyl group substituent.
  • alkanols include but are not limited to methanol, ethanol, 1 - and 2-propanol, 1,1- dimethylethanol, hexanol, octanol and the like.
  • Alkanol groups may be optionally substituted with substituents as described above.
  • alkenol or "alkenol group” refers to a compound including an alkene 2 to 20 carbon atoms or more having at least one hydroxyl group substituent. The hydroxyl may be arranged in either isomeric configuration (cis or trans). Alkenols may be further substituted with one or more substituents as described above and may be used in place of alkenols in some embodiments of the invention. Alkenols are known to those skilled in the art and many are readily available commercially.
  • the term "about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%.
  • LOI limiting oxygen index
  • ASTM D2863 provides quantitative information about a material's ability to burn or "ease of burn”. If a polymeric material has an LOI of at least 27, it will, generally, bum only under very high applied heat.
  • Fire resistance may also be tested both by measuring the 02 index in accordance with ASTM D 2863-70 and also by measuring the after-burning time in accordance with the UL test (Subject 94).
  • the tested materials are given classifications of UL-94 VO, UL-94 VI and UL-94 V2 based on the results obtained with the ten test bars of a given thickness. Briefly, the criteria for each of these UL-94V-classifications are as follows:
  • UL-94 V2 the total flaming combustion for each specimen after removal of the ignition flame should not exceed 30 seconds and the total flaming combustion for 5 specimens should not exceed 250 seconds. Test specimens may release flaming particles, which ignite absorbent cotton wool.
  • Fire resistance may also be tested by measuring after-burning time.
  • These test methods provide a laboratory test procedure for measuring and comparing the surface flammability of materials when exposed to a prescribed level of radiant heat energy to measure the surface flammability of materials when exposed to fire. The test is conducted using small specimens mat are representative, to the extent possible, of the material or assembly being evaluated. The rate at which flames travel along surfaces depends upon the physical and thermal properties of the material, product or assembly under test, the specimen mounting method and orientation, the type and level of fire or heat exposure, the availability of air, and properties of the surrounding enclosure. If different test conditions are substituted or the end-use conditions are changed, it may not always be possible by or from mis test to predict changes in the fire-test-response characteristics measured. Therefore, the results are valid only for the fire test exposure conditions described in this procedure.
  • Both number average (Mn) and weight average molecular weight (Mw) as used herein, can be determined by gel permeation chromatography (GPC).
  • GPC provides information about the molecular weight and molecular weight distribution of a polymer based on size exclusion chromatography.
  • the molecular weight of a polymer is based on the calibration of the chromatograph columns using known molecular weights of polystyrene standards. It is known mat the molecular weight distribution of a polymer is important to properties such as thermo-oxidative stability (due to different amount of end groups), toughness, melt flow, and fire resistance, for example, low molecular weight polymers drip more when burned.
  • Embodiments of the invention are not limited by the type of phosphonate component included and may include, for example, polyphosphonates, branched polyphosphonates, or hyberbranched polyphosphonates, random or block copolyphosphonates, co-oligo(phosphonate ester)s, or co-oligo(phosphonate carbonate)s, phosphonate oligomers, branched phosphonate oligomers, or hyperbranched phosphonates, and in certain embodiments, the phosphonate component may have the structures described and claimed in U.S. Patent Nos. US7,645,850, US7,816,486, US8,389,664, US8,563,638, US8,648,163, US8,779,041, US8,530,044, each of which is hereb>' incorporated by reference in its entirety.
  • Such phosphonate components may include repeating units derived from diaryl alkylphosphonates or diaryl arylphosphonates.
  • such phosphonate components include structural units illustrated by Formula I:
  • Ar is an aromatic group and -O-Ar-0- may be derived from an aromatic dihydroxy compound or aromatic diol
  • R is a Ci -20 alkyl, C2-20 alkene, C2-20 alkyne, C5-20 cycloalkyl, or C&.20 aryl
  • nl is an integer from 2 to about 200, 2 to about 100, 2 to about 75, 2 to about 50, 2 to about 20, 2 to about 10, or 2 to about 5, or any integer between these ranges.
  • aromatic diol is meant to encompass any aromatic or predominately aromatic compound with at least two associated hydroxyl substitutions of the formula ( ⁇ )
  • n2, p2, and q2 are each independently 0, 1, 2, 3, or 4; Ra is independently at each occurrence unsubstituted or substituted CMO hydrocarbyl; and X" is a single bond,— O— ,— S— ,— S(0>— ,— S(0)2— ,— C(0>— , or a Cuis hydrocarbylene, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise one or more heteroatoms selected from oxygen, nitrogen, sulfur, silicon, or phosphorus.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen unless it is specifically identified as "substituted hydrocarbyl".
  • the hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • substituted means including at least one substituent such as a hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, CMS alkyl, CMS alkoxyl, Ce-it aiyl, Ce-is aryloxyl, C7-18 alkylaryl, or C7-18 alkylaryloxyl.
  • substituents i.e., F, CI, Br, I.
  • dihydroxy compounds include the following: bisphenol compounds such as 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7- dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxy-3,5-dimemylphenyl)methane, bis(4- hydroxy-3,5-dichlorophenyl)methane, bis(4-hydrox>'-3,5-dibromophenyl)methane, bis(4- hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3-chlorophenyl)methane, bis(4- hydroxyphenyl
  • the Ar may be derived from bisphenol A and R may be a methyl group providing polyphosphonates, phosphonate copolymers, random and block co-oligo(phosphonate carbonate)s and co-oligo(phosphonate ester)s, and oligomeric phosphonates that may have structures such as, but not limited to, structures of Formulae III:
  • a single aromatic diol may be used, and in other embodiments, various combinations of such aromatic diols may be incorporated into the polymer.
  • the phosphorous content of phosphonate component may be controlled by the molecular weight (MW) of the aromatic diol used in the oligomeric phosphonates, polyphosphonates, or copolyphosphonates.
  • MW molecular weight
  • a lower molecular weight aromatic diol may produce an oligomeric phosphonate, polyphosphonate, or copolyphosphonate with a higher phosphorus content.
  • An aromatic diol such as resorcinol, hydroquinone, or a combination thereof or similar low molecular weight aromatic diols may be used to make oligomeric phosphonates or polyphosphonates with high phosphorous content
  • the phosphorus content, expressed in terms of the weight percentage, of the phosphonate oligomers, phosphonates, or copolyphosphonates may be in the range from about 2 wt. % to about 18 wt. %, about 4 wt. % to about 16 wt. %, about 6 wt. % to about 14 wt. %, about 8 wt. % to about 12 wt. %, or a value between any of these ranges.
  • phosphonate oligomers, polyphosphonates, or copolyphosphonates prepared from bisphenol A or hydroquinone may have phosphorus contents of 10.5 wt. % and 18 wt. %, respectively.
  • the phosphonate component may be a polyphosphonate containing long chains of the structural unit of Formula I.
  • the polyphosphonates may have a weight average molecular weight (Mw) of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the polyphosphonates may have an Mw of from about 12,000 to about 80,000 g/mole as determined by GPC.
  • the number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole.
  • the molecular weight distribution (i.e., Mw/Mn) of such polyphosphonates may be from about 2 to about 10 in some embodiments and from about 2 to about 5 in other embodiments.
  • the phosphonate component may be a polyphosphonate containing branched structures of the structural unit of Formula I.
  • a branching agent i.e. tri or tetrahydroxy aromatic compound
  • the branched polyphosphonates may have a molecular weight distribution (i.e., Mw/Mn) of from about 2 to about 10 in some embodiments and from about 2.3 to about 3.2 in other embodiments.
  • the phosphonate component may be copolymers containing carbonate linkages [i.e., copoly(phosphonate carbonate)] or ester linkages [i.e., copoly (phosphonate esters)].
  • copoly(phosphonate carbonate)s may include repeating units derived from at least 20 mole percent high purity diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more diaryl carbonate, and one or more aromatic dihydroxy compounds, wherein the mole percent of die high purity diaryl alkylphosphonate is based on the total amount of transesterification components, i.e., total diaryl alkylphosphonate and total diaryl carbonate.
  • random the monomers of the copoly(phosphonate carbonate)s of various embodiments may be incorporated into polymer chain randomly.
  • the polymer chain may include alternating phosphonate and carbonate monomers linked by one or more aromatic dihydroxide and/or various segments in which several phosphonate or several carbonate monomers form phosphonate or carbonate segments. Additionally, the length of various phosphonate or carbonate segments may vary within individual copoly(phosphonate carbonate)s.
  • the phosphonate and carbonate content of the copoly(phosphonate carbonate)s may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content.
  • the copoly(phosphonate carbonate)s may have a phosphorus content of from about 1% to about 20% by weight of the total copoly (phosphonate carbonate), and in other embodiments, the phosphorous content of the copoly(phosphonate carbonate)s of the invention may be from about 2% to about 10% by weight of the total polymer.
  • the copoly(phosphonate carbonate)s or copoly(phosphonate ester)s may have structures such as, but not limited to, those structures of Formulae IV and V, respectively:
  • Ar 1 and Ar 2 are each, independently, an aromatic group and -O-Ar'-O- and -O-Ar -O- may be derived from a dihydroxy compound as described by structure (II).
  • R is a Ci-20 alkyl, C2.20 alkene, C2-20 alkyne, Cj.20 cycloalkyl, or Ce-2o aryl.
  • Rl may be a Ci-20 alkylene or cycloalkylene, such as methylene, ethylene, propylene, butylene, pentylene, and the like, and in particular embodiments, R 1 can be derived from aliphatic diols such as, but not limited to, 1,4-cyclohexyldimethanol, 1,4-butane diol, 1,3- propane diol, ethylene diol, ethylene glycol, and the like and combinations thereof.
  • R2 is, independently, a d-20 alkylene, C2-20 alkylenylene, C2-20 alkylynylene, C5.20 cycloalkylene, or Ce-20 arylene, each Zi is, independently, d-20 alkylene, C2.20 alkylenylene, C2-20 alkylynylene, d-20 cycloalkylene, or d-20 arylene.
  • R 2 can be derived from adipic acid, dimethyl terephthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and the like or derivatives thereof or combinations thereof.
  • R 2 may be an aromatic group such as naphthalene, phenylene, biphenylene, propane-2,2- diyldibenzylene, and in some embodiments, R 2 can be derived from, for example, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, and the like and combinations thereof.
  • R 2 may be, for example, naphthalene, phenyl, both of which may be substituted at any position on the rings.
  • Such copoly(phosphonate carbonates) or copoly(phosphonate esters) may be block copoly(phosphonate carbonates) or copoly(phosphonate esters) in which each m, n, and p is greater than about 1, and the copolymers contain distinct repeating phosphonate and carbonate blocks or phosphonate and ester blocks.
  • the copoly(phosphonate carbonates) or copoly(phosphonate esters) can be random copolymers in which each m4, n4, and pS are each, independently, an integer from 1 to about 200, 1 to about 100, 1 to about 75, 1 to about 50, 1 to about 20, 1 to about 10, or 1 to about 5, or any integer between these ranges.
  • the Ar 1 and Ar 2 may be derived from bisphenol A and R may be a methyl group providing random and block co(phosphonate carbonate)s and co(phosphonate ester)s that may have structures such as, but not limited to, structures of Formulae VI and VII:
  • the copoly(phosphonate carbonate)s of various embodiments exhibit bom a high molecular weight and a narrow molecular weight distribution (i.e., low polydispersity).
  • the copoly(phosphonate carbonate)s may have a weight average molecular weight (Mw) of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the copoly(phosphonate carbonate)s may have a Mw of from about 12,000 to about 80,000 g/mole as determined by GPC.
  • the number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole.
  • the narrow molecular weight distribution (i.e., Mw/Mn) of such copoly(phosphonate carbonate)s may be from about 2 to about 7 in some embodiments and from about 2 to about 5 in other embodiments.
  • the molecular weight (weight average molecular weight as determined by gel permeation chromatography based on polystyrene calibration) range of the oligophosphonates, random or block co-oligo(phosphonate ester)s and co- oligo(phosphonate carbonate)s may be from about 500 g/mole to about 18,000 g/mole or any value within this range. In other embodiments, the molecular weight range may be from about 1,500 g/mole to about 15,000 g/mole, about 3,000 g/mole to about 10,000 g/mole, or any value within these ranges.
  • the molecular weight range may be from about 700 g/mole to about 9,000 g/mole, about 1,000 g/mole to about 8,000 g/mole, about 3,000 g/mole to about 4,000 g/mole, or any value within these ranges.
  • the oligomeric phosphonates can have about 60% to about 100% of the total of oligomeric phosphonates have two or more reactive end-groups. In other embodiments, about 75% to about 99% of the total of oligomeric phosphonates have two or more reactive end-groups.
  • the reactive end-groups may be, for example, epoxy, vinyl, vinyl ester, isopropenyl, isocyanate, or combinations thereof, and in certain embodiments, about 80% to about 100% of the total oligomeric phosphonates may have two or more hydroxyl end groups.
  • the oligomeric phosphonates or portions thereof may include oligophosphonate, random co- oligo(phosphonate ester), block co-oligo(phosphonate ester), random co-oligo(phosphonate carbonate), block co-oligo(phosphonate carbonate), or combinations thereof.
  • the oligomeric phosphonates may include linear oligomeric phosphonates, branched oligomeric phosphonates, or a combination thereof, and in other embodiments, such oligomeric phosphonates may further include hyperbranched oligophosphonates.
  • polymer composition refers to a composition that comprises at least one of the present inventions and at least one other polymer, oligomer, or monomer mixture.
  • the other polymer, oligomer, or monomer mixture may include those that comprise, or are partially comprised of, or are comprised of monomers intended to produce the following polymer families including but not limited to a polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyether, polyamide, polystyrene, polyurethane, polyurea, polyurethane urea, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), polyethylene, polypropylene, polyphenylene sulfide, polyvinyl ester), polyvinyl chloride, bismaleimide polymer, poly anhydride, liquid crystalline polymer, cellulose polymer, benzoxazine resin, another polyphosphonate, or a
  • Any epoxy resin can be used for the purpose(s) of the invention provided that the resin contains at least one glycidyl group, alicyclic epoxy group, or a similar epoxy group (i.e., oxirane or ethoxyline group).
  • the resin contains at least one glycidyl group, alicyclic epoxy group, or a similar epoxy group (i.e., oxirane or ethoxyline group).
  • a similar epoxy group i.e., oxirane or ethoxyline group.
  • an epoxy resin having two or more epoxy groups is preferred.
  • Such a component can be represented by novolac-type epoxy resin, cresol- novolac epoxy resin, triphenolalkane-type epoxy resin, aralkyl-type epoxy resin, aralkyl-type epoxy resin having a biphenyl skeleton, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, heterocyclic-type epoxy resin, epoxy resin containing a naphthalene ring, a bisphenol-A type epoxy resin, a methylene dianiline type epoxy resin, a bisphenol-F type epoxy compound, stilbene-type epoxy resin, trimethylol-propane type epoxy resin, terpene- modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracetic acid or a similar peracid, alicyclic epoxy resin, or sulfur-containing epoxy resin.
  • the substrate may also be composed of two or more epoxy resins of the aforementioned types.
  • Preferable epoxy resins are those derived from bisphenol A or methylene dianiline.
  • Preferable for use are aralkyl-type epoxy resins with a biphenyl structure, a bisphenol A structure or a methylene dianiline structure.
  • the epoxy resin is typically commercially available, though this is not a requirement for applicability.
  • the epoxy may also contain as a component a benzoxazdne compound, oligomer or resin.
  • the polymer compositions of the present invention may comprise other components, such as but not limited to other flame retardants, chopped or continuous glass, metal, carbon based, or ceramic fibers; fillers, surfactants, mold release agents, organic binders, polymeric binders, crosslinking agents, coupling agents, anti- dripping agents, colorants, inks, dyes, antioxidants or other stabilizers, or any combination thereof.
  • other components such as but not limited to other flame retardants, chopped or continuous glass, metal, carbon based, or ceramic fibers; fillers, surfactants, mold release agents, organic binders, polymeric binders, crosslinking agents, coupling agents, anti- dripping agents, colorants, inks, dyes, antioxidants or other stabilizers, or any combination thereof.
  • the present invention can be used as coatings on plastics, metals, ceramic, or wood products or they can be used to fabricate articles, such as free-standing films and extruded sheets, fibers, foams, molded articles, adhesives, filaments, and fiber reinforced composites. These articles may be well-suited for applications requiring fire resistance.
  • the present invention and polymer compositions including them exhibit outstanding flame resistance and good melt processability. Such improvements make these materials useful in applications in the automotive and electronic sectors that require outstanding fire retardancy, high temperature performance, and melt processability.
  • CNTs Carbon nanotubes
  • CNTs are allotropes of carbon with a cylindrical nanostructure. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics, optics, and other fields of materials science and technology.
  • CNTs have extraordinary thermal conductivity' and mechanical and electrical properties making them suitable as additives to various structural materials.
  • Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Either or mixtures of the two may be used in the compositions described herein.
  • the CNTs are typically added to polymer blends in the form of a master batch.
  • the carrier for these masterbatches preferably is the same as the target polymer.
  • a masterbatch of CNT in PC is added to PC.
  • PET applications a masterbatch of CNTs in PET is used.
  • polyphosphonates as flame retardants has the advantage that, because of the polymeric nature of the polyphosphonates, these can be used as carrier in a CNT masterbatch. This has the advantage that such a CNT masterbatch can be applied in any polymer system, PC, PET, etc.
  • PLASTICYL PC 1501 Polycarbonate polymer containing 15wt% short tangle multiwall carbon nanotubes (MWCNTs) (Nanocyl S.A., Belgium)
  • Nofia CO6000, HM1100, and HM9000 phosphonate (copolymers (FRX Polymers, USA).
  • Lexan 101 and Lexan 141 Polycarbonate (SABIC, USA).
  • a 27 millimeter twin screw extruder was used to compound a variety of compositions of polycarbonate, Nofia polyphosphonates and CNTs.
  • the temperature of the extruder was set at 200 °C at the feeding block, and the subsequent zones were set at various temperatures to study their effect on the blend, e.g. from 210 °C to 240 °C.
  • the compounding was conducted at 20 lbs/hour with a screw speed of 100 rpm All ingredients were used as received without drying and mixed before putting into the feed hopper.
  • Melt volume ratio was measured on Dynisco LMI 4000 Melt Indexer.
  • a screening method was developed within FRX Polymers (FRXP, FIGURE 1).
  • the specimen (3.2 mm thick, 150 mm x 150 mm) was mounted onto a devise as shown in the picture.
  • Table 1 shows the effect of CNT loading on the burning behavior of blends of PC and polyphosphonates. As shown in Table 1, a certain amount of CNT is needed to effectively prevent melting or sagging of molten polymer mass. At 0.53% of CNT no sagging or melting of the polymer occurs for 3.2mm thick samples containing PC and 35wt% of polyphosphonate.
  • FIG. 2A shows CEX 1 after burning.
  • FIG. 2B and FIG. 2C show the front and back view of EX 2 after burning, respectively. It can be seen that in CEX 1 a hole was formed due to melting and dripping/sagging of the molten polymer mass, while in EX 2 no hole was formed and char formation took place instead.
  • Ultem 1010 an inherently flame retardant polymer, is one of the few thermoplastic polymers that passes the OSU test according to FAR 25.853. Here it is used as positive control. As shown in FIG 3, a sample made from Ultem 1010 looks very similar to EX 2 and has a very similar melting/sagging behavior as EX 2.
  • Table 2 shows the effect of polyphosphonate loading in the PC/CNT blends. Without polyphosphonate, the specimen will still melt away to form holes. Furthermore, the material continues to burn after the five minutes exposure. With increasing the polyphosphonate loading, the burning time is reduced and less melting/sagging is also observed. In these experiments, about 30% of Nofia HM1100, i.e. a composition with a P content of about 3.2%, is needed to effectively prevent dripping and after burn.
  • Table 3 shows the effect of polyphosphonate grade. As shown in Table 3, lower viscosity (higher MVR) polyphosphonate grade led to more melting/sagging of the materials during burning.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des mélanges de polyphosphonates avec des nanotubes de carbone (NTC), des mélanges de polycarbonate et de polyphosphonate avec des NTC et des procédés de fabrication et d'utilisation de ceux-ci, ainsi que des articles fabriqués à partir de ceux-ci. Dans certains modes de réalisation, l'invention concerne des articles, tels que des feuilles et des films, fabriqués à partir de tels mélanges. Les mélanges et articles fabriqués à partir de ceux-ci présentent des propriétés ignifuges.
PCT/US2019/019396 2018-02-23 2019-02-25 Compositions de polyphosphonates et de nanotubes de carbone WO2019165359A1 (fr)

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US62/634,614 2018-02-23

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US8044127B2 (en) * 2002-01-30 2011-10-25 Idemitsu Kosan Co., Ltd. Thermoplastic resin composition, polycarbonate resin composition, and molded article thereof
US20130203928A1 (en) * 2010-09-07 2013-08-08 Bayer Intellectual Property Gmbh Process for producing polymer-cnt composites
US20150017577A1 (en) * 2013-07-11 2015-01-15 Xerox Corporation Imaging members having a cross-linked anticurl back coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8044127B2 (en) * 2002-01-30 2011-10-25 Idemitsu Kosan Co., Ltd. Thermoplastic resin composition, polycarbonate resin composition, and molded article thereof
US20130203928A1 (en) * 2010-09-07 2013-08-08 Bayer Intellectual Property Gmbh Process for producing polymer-cnt composites
US20150017577A1 (en) * 2013-07-11 2015-01-15 Xerox Corporation Imaging members having a cross-linked anticurl back coating

Non-Patent Citations (1)

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"Carbon nanotube", WIKIPEDIA, 25 November 2017 (2017-11-25), XP055631686, Retrieved from the Internet <URL:https://en.wikipedia.org/w/index.php?title=Carbon_nanotube&oldid=812034359> [retrieved on 20190425] *

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