WO2019060657A1 - Procédé de production de poudre de polycarbonate semi-cristalline avec un retardateur de flamme ajouté pour la fusion de poudre et applications de composites - Google Patents

Procédé de production de poudre de polycarbonate semi-cristalline avec un retardateur de flamme ajouté pour la fusion de poudre et applications de composites Download PDF

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WO2019060657A1
WO2019060657A1 PCT/US2018/052120 US2018052120W WO2019060657A1 WO 2019060657 A1 WO2019060657 A1 WO 2019060657A1 US 2018052120 W US2018052120 W US 2018052120W WO 2019060657 A1 WO2019060657 A1 WO 2019060657A1
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polycarbonate
powder
solvent
flame retardant
phosphorous
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PCT/US2018/052120
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English (en)
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Kapil INAMDAR
Chiel Albertus Leenders
Haimanti DATTA
Rudolf Martinus Petrus VAN DER HEIJDEN
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Sabic Global Technologies B.V.
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Publication of WO2019060657A1 publication Critical patent/WO2019060657A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • 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
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • This application relates to methods for producing a crystalline polycarbonate powder incorporating a phosphorous-containing flame retardant, and the crystalline
  • This application also relates to methods of using the crystalline polycarbonate powder in additive manufacturing and in manufacturing fiber reinforced polycarbonate composites, and the additive manufacturing products and fiber reinforced polycarbonate composite products made using the powders.
  • additive manufacturing also known in the art as "three-dimensional” or “3D” printing
  • additive manufacturing is a process for the manufacture of three-dimensional objects by formation of multiple fused layers.
  • AM methods that can be conducted using thermoplastic polymers such as polycarbonate include material extrusion (ME), for example fused deposition modelling, and powder bed fusing.
  • ME material extrusion
  • powder bed fusing thermal energy selectively fuses regions of a powder bed.
  • SLS selective laser sintering
  • Preferred powders for these processes have of a uniform shape, and size and composition.
  • thermoplastic polymers economically on a large scale
  • amorphous polycarbonates particularly in powder bed fusing processes such as SLS because they do not have a sharp melting point.
  • This property causes the applied thermal energy source (e.g., a laser beam) to be dissipated into the regions surrounding where the energy beam strikes the bed.
  • This undesired dissipation of thermal energy can cause unstable processing as well as poor feature resolution in the intended three-dimensional articles being produced.
  • preparation of crystalline polycarbonate having the desired particle sizes, particularly for powder bed fusion is particularly difficult.
  • fiber reinforced composites can be produced using fibers (such as carbon fibers that are in milled, chopped, woven, or continuous form) combined with a polymer matrix of choice.
  • the fibers primarily serve as the load bearing structural components, with the surrounding polymer matrix holding the fibers together and transferring load between the fibers.
  • thermoplastic polymer tapes One such method, referred to as the "aqueous process," uses a thermoplastic polymer in fine powder form dispersed in water using a suitable surfactant.
  • Continuous fibers are pulled through the aqueous dispersion and combined with the polymer particles followed by evaporation of water, melting of the polymer that is captured within the continuous fibers, and consolidation of the fiber-polymer combination by pulling through a heated die to provide a composite product with the desired fiber content, width, and thickness.
  • This aqueous process relies on using the powder form of the thermoplastic polymer to produce high fiber volume fraction UD tapes.
  • a key to producing high quality UD tapes with the aqueous process is use of a fine polymer particle size, for example particles sizes having a D50 of 20 to 45 micrometers or a D 100 of below 80 micrometers.
  • Polymer particle size and distribution outside the desired range can have detrimental effects on the UD tape process, including lower throughputs and yields, and reduced process continuity, as well as the UD tape products, including less homogenous composition, non-uniform appearance/finish, splits, or tears in the fiber direction, and high void content. These can require additional processing efforts during production of the composite structure, as well as lower part performance.
  • a method of preparing a partially crystalline polycarbonate powder containing a phosphorous-containing flame retardant includes: dissolving an amorphous polycarbonate and a phosphorous-containing flame retardant in a halogenated alkane solvent to form a solution; combining the solution with a crystallizing non-solvent that is miscible with the halogenated alkane solvent; and mixing the combined solution and crystallizing non- solvent under high shear mixing conditions effective to form a partially crystalline polycarbonate precipitate.
  • FIG. 1 is a schematic of a process to produce polycarbonate/flame retardant powder using a solvent, a non-solvent, and filtration as the means for removing the precipitate.
  • FIG. 2 is a schematic of another process to produce polycarbonate/flame retardant powder using a solvent, a non-solvent, and evaporation as the means for removing the precipitate.
  • FIG. 3 is a graph of initial versus final RDP content in FR-PC powder is using the filtration removal technique of FIG. 1.
  • FIG. 4 is a graph showing reduction in Tg as function of phosphorous content.
  • FIG. 5 is a graph of initial versus final RDP content in FR-PC powder is using the evaporation removal technique of FIG. 2.
  • the method includes dissolving the amorphous polycarbonate and the phosphorous-containing polycarbonate in a solvent, and subsequently combining the solution with a crystallizing non-solvent while applying high speed mixing to form a precipitate.
  • the precipitate can be used as the powder directly after isolation.
  • the flame retardant is incorporated primarily within the powder particles, which can provide greater stability and more consistent processability.
  • the method can further have one or more of the following advantages.
  • a partially crystalline polycarbonate powder can be precipitated having good crystallinity, particle size distribution, and flowability. All or most of the particles of the partially crystalline polycarbonate powder can have an average or absolute particle size of less than 150 micrometers ( ⁇ ).
  • the partially crystalline polycarbonate powder can therefore be effectively used in powder bed fusion processes, e.g., selective laser sintering processes, to produce layers having a thickness of 100 ⁇ to 150 ⁇ .
  • the presence of the FR additive in the partially crystalline polycarbonate powder is especially useful in the manufacture of articles where flame retardancy meets an additional critical need, for example in UD tapes produced for the consumer electronics industry market.
  • amorphous and crystalline as used herein are generally in accordance with their usual meanings in the polymer art.
  • an amorphous polycarbonate the molecules can be oriented randomly and can be intertwined, and the polymer can have a glasslike, transparent appearance.
  • crystalline polycarbonates the polymer molecules are aligned together in ordered regions. It is to be understood, however, that the process described herein can be used with a polycarbonate composition that is either fully amorphous, or that contains both amorphous and crystalline polycarbonate; and that the process is useful even when only a portion of the amorphous polycarbonate is converted to crystalline polycarbonate.
  • amorphous polycarbonate is used herein to denote a starting polycarbonate wherein at least a portion of the polycarbonate is in an amorphous form.
  • One preferred embodiment is to start with fully amorphous (i.e., 100% amorphous)
  • polycarbonate and the term "partially crystalline" is used herein to denote a product polycarbonate wherein at least a portion of the amorphous form in the starting material has been converted to the crystalline form in the product.
  • the portion of the amorphous form in the starting material has been converted to the crystalline form is not more than 45%
  • polycarbonate powder that contains a flame retardant includes dissolving an amorphous polycarbonate and a phosphorus-containing flame retardant in a halogenated alkane solvent to provide a solution.
  • amorphous polycarbonate and the phosphorus-containing flame retardant components are described in detail further below.
  • Suitable halogenated alkanes include, for example, C 1-6 alkanes comprising at least one halogen (preferably chlorine, fluorine, or a combination comprising at least one of the foregoing), preferably at least two halogens (preferably chlorine, fluorine, or a combination comprising at least one of the foregoing).
  • Preferred solvents include dichloromethane, chloroform, methylene chloride or a combination comprising at least one of the foregoing solvents.
  • the amount of halogenated alkane solvent can be sufficient to form both a solution of the amorphous polycarbonate and the flame retardant as well as a precipitated mixture after the crystallizing non- solvent is added as described below.
  • the amount with the type and amount of polycarbonate, type and amount of flame retardant and type and amount of halogenated alkane solvent and crystallizing non-solvent used, as well as the particular manufacturing process conditions used is also described below.
  • the amount of a halogenated alkane solvent can be 100 to 1000 wt%, based on the weight of amorphous polycarbonate, or 200 to 500 wt%, based on the weight of amorphous polycarbonate.
  • the phosphorus-containing flame retardant can be dissolved in the halogenated solvent before the amorphous polycarbonate, or added to the solvent simultaneously with the polycarbonate (individually or already incorporated in the polycarbonate), or added to the solvent in a next sequential step after the polycarbonate or after the polycarbonate is dissolved. Dissolution can be conducted at ambient temperature or slightly elevated temperature.
  • the crystallizing non-solvent is selected to be miscible with the halogenated alkane solvent, and to provide a partially crystalline product under high shear conditions.
  • the crystallizing non- solvent can be a ketone such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), or the like.
  • the amount of crystallizing non- solvent can be an amount sufficient to form the partially crystallized polycarbonate/ flame retardant precipitate, and can vary with the type and amount of
  • the amount of crystallizing non-solvent is from 100 to 1000 wt%, based on the weight of amorphous polycarbonate, or from 200 to 500 wt%, based on the weight of amorphous polycarbonate.
  • the solution of amorphous polycarbonate and flame retardant is added dropwise or as a slow stream over a period of time to the crystallizing non- solvent while agitating under high shear mixing conditions to form the precipitate.
  • the crystallizing non-solvent is added quickly to the solution of amorphous polycarbonate and flame retardant.
  • the duration of the addition can be, for example, 1 minute to ten hours or 5 minutes to 1 hour, and can depend on the total volumes being combined.
  • high shear mixing refers to methods of agitating the components in a mixture (e.g. liquid mixture) under conditions in which high shear forces are generated.
  • a high shear mixer creates patterns of flow and turbulence, generally using an impellor that rotates inside a stator. Once the impellor has drawn mixture in, it subjects the mixture sudden changes of direction and acceleration, often approaching 90 degrees, such that the mixture contacts the wall of the stator with centrifugal force, or is forced through the holes in the stator at great pressure and speed, in a final disintegrating change of direction and acceleration.
  • the high shear mixing comprises mixing at speeds of 2,000 rotations per minute (rpm) to 50,000 rpm, specifically, 10,000 rpm to 30,000 rpm, more specifically 15,000 rpm to 25,000 rpm.
  • High shear mixing can be achieved with any commercially available high shear mixers.
  • a high shear mixer such as a Silverson L5M homogenizer or an IKA T-25 Ultraturrax can be used.
  • the duration of the high shear mixing can depend upon the properties desired in the partially crystalline polycarbonate/flame retardant powder composition. In some embodiments, the mixing is from 1 minute to 10 hours, or from 10 minutes to 5 hours, or from 10 minutes to 1 hour. The mixing can be carried out in-line or batch. The process can readily be carried out at manufacturing scale. The flame retardant is incorporated into the partially crystallized polycarbonate structure.
  • the halogenated alkane and crystallizing non- solvent are removed from the solid polycarbonate/ flame retardant precipitate to provide an isolated polycarbonate/ flame retardant precipitate.
  • the removing of the halogenated alkane solvent and the crystallizing non-solvent from the precipitate comprises filtering the precipitate. Any suitable filtration technique can be used.
  • the removing the halogenated alkane solvent and the crystallizing non-solvent from the precipitate comprises at least partially evaporating the solvents from the precipitate. Any suitable evaporation technique can be used.
  • a rotary evaporator such as a RotavaporTM evaporator is one type of suitable evaporation apparatus. It has unexpectedly been found that use of evaporation improves the incorporation of the flame retardant into the polycarbonate particles.
  • the halogenated alkane solvent is dichloromethane
  • crystallizing non- solvent is methyl ethyl ketone
  • the removing the halogenated alkane solvent and the crystallizing non- solvent from the precipitate comprises at least partially evaporating the solvents from the precipitate.
  • the isolated polycarbonate/ flame retardant precipitate can be optionally dried at ambient temperature or by heating, either being with or without vacuum. As described above, the isolated and optionally dried precipitate can be used directly as the partially crystalline polycarbonate powder. Alternatively, the isolated and optionally dried precipitate can be further processed to provide the partially crystalline polycarbonate powder. For example, if
  • the agglomerates can be broken by crushing, high speed mixing, milling, or other low- to high-force shearing processes to form the partially crystalline polycarbonate powder.
  • Polycarbonate as used herein means a homopolymer or copolymer having repeating structural carbonate units of formula (1)
  • each R 1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).
  • each R is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a C 6 -io aryl, or a halogen-substituted C6-io aryl, and n is 0 to 4.
  • R a and R b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl
  • p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen.
  • p and q is each 0, or p and q is each 1, and R a and R b are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.
  • X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-18 organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • dihydroxy compounds that can be used are described, for example, in WO 2013/175448 Al, US 2014/0295363 and WO 2014/072923. Specific dihydroxy
  • compounds that can be used include resorcinol, 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A” or “BPA”), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, "PPPBP”, or 3,3-bis(4- hydroxyphenyl)-2-phenylisoindolin- 1 -one) , 1,1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, and l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).
  • Polycarbonate copolymers can include different types of carbonate units or repeat units different from the carbonate units, for example ester units, siloxane units, or the like.
  • poly(ester-carbonate)s further contain, in addition to repeat carbonate chain units of formula (1), repeat ester units of formula (4)
  • J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a C2-10 alkylene, a C 6 -20 cycloalkylene, a C 6 -20 arylene, or a polyoxy(C2-6alkyl)ene
  • T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a C2-20 alkylene, a C 6 -20 cycloalkylene, or a C 6 -20 arylene.
  • Copolyesters containing a combination of different T or J groups can be used.
  • the polyester units can be branched or linear.
  • Specific dihydroxy compounds include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a C 1-8 aliphatic diol such as ethane diol, n-propane diol, i- propane diol, 1,4-butane diol, 1,6-cyclohexane diol, 1,6-hydroxymethylcyclohexane, or a combination comprising at least one of the foregoing dihydroxy compounds.
  • aromatic dihydroxy compounds of formula (2) e.g., resorcinol
  • bisphenols of formula (3) e.g., bisphenol A
  • a C 1-8 aliphatic diol such as ethane diol, n-propane diol, i- propane diol, 1,4-butane diol, 1,6-cyclohexane diol, 1,6-hydroxymethylcyclohexane, or a combination compris
  • Aliphatic dicarboxylic acids that can be used include C 6 -20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), specifically linear Cs-i2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Ci2 dicarboxylic acids such as dodecanedioic acid (DDDA).
  • Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,6-cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids.
  • a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.
  • Specific ester units include ethylene terephthalate units, n-propylene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A.
  • the molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary broadly, for example 1:99 to 99: 1, specifically, 10:90 to 90: 10, more specifically, 25:75 to 75:25, or from 2:98 to 15:85.
  • poly(siloxane-carbonate)s include repeat carbonate units of formula (1) and repeat siloxane units as are known in the art and described, for example, in U.S. Pat. No. 9,598,578 and U.S. Pat. No. 8,466,249.
  • Poly(siloxane-ester-carbonate)s can also be used, for example poly(ITR-dimethyl siloxane-bisphenol A carbonate)s as described in U. S. Pat. No. 9,266,541.
  • the polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), specifically 0.45 to 1.0 dl/gm.
  • polycarbonates can have a weight average molecular weight of 5,000 to 200,000 Daltons, specifically 15,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to Bisphenol A
  • GPC samples are prepared at a concentration of 1 mg per ml (mg/ml), and are eluted at a flow rate of 1.5 ml per minute.
  • the types of phosphorus-containing compounds useful as flame retardants can vary greatly.
  • the phosphorus-containing flame retardant is an organic compound that includes an aromatic group, a phosphorus -nitrogen bond, or a combination comprising at least one of the foregoing.
  • Non-brominated and non-chlorinated phosphorus-containing flame retardants can be preferred in certain applications for regulatory reasons.
  • the phosphorus- containing flame retardant includes an phosphate, phosphite, phosphonate, phosphinate, phosphine oxide, or phosphine, each containing a C3-30 aromatic group optionally comprising up to three heteroatoms in an aromatic ring, a phosphazene, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, tris(aziridinyl) phosphine oxide, or a combination comprising at least one of the foregoing. Any of the foregoing compounds can be monomeric or polymeric.
  • Two of the G groups may be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate, which is described by Axelrod in U.S. Pat. No. 4,154,775.
  • a suitable aromatic phosphate can be phenyl bis(dodecyl)phosphate, phenyl
  • a specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate
  • di- or polyfunctional aromatic phosphorus -containing compounds are also useful, for example, compounds of the formulas below: wherein each G 1 is independently a Ci-30 hydrocarbyl; each G 2 is independently a Ci-30 hydrocarbyl or hydrocarbyloxy; X a is as defined in formula (3); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30.
  • Di- or polyfunctional aromatic phosphorus- containing compounds of this type include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, their oligomeric and polymeric counterparts, and the like.
  • RDP resorcinol tetraphenyl diphosphate
  • the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A
  • their oligomeric and polymeric counterparts and the like.
  • the phosphorus-containing flame retardant can be a linear or cyclic polyphosphonate homopolymer or copolymer, such as those described in U.S. Patent No. 6,861,499 and 7,816,486.
  • Polyphosphonates can exhibit at least one of a broad molecular weight distribution with polydispersity of 3.2 or greater, 2.5 or greater, and 2.3 or greater, an Mw of greater than 10,000 grams per mole (as measured using polystyrene standards), and a Tg of at least 100°C.
  • the polyphosphonates can have a Tg of 25 to 140°C, or 50 to 135°C, or 75 to 130°C.
  • the polyphosphonates can be prepared from an aryl phosphonic acid ester and either bisphenol A or a mixture of bisphenol A and another bisphenol in the presence of a phosphonium catalyst or an alkaline metal catalyst such as a sodium catalyst.
  • the polyphosphonates can have a relative viscosity of at least 1.1,
  • Exemplary polyphosphonate copolymers include poly(phosphonate-carbonate)s, which can be block or random copolymers.
  • the polyphosphonate copolymers can have a phosphorus content of 1 to 15 weight percent (wt%) of the total copolyphosphonate, for example 1 to 12 wt%, or 2 to 10 wt%.
  • the organic compound containing a phosphorus -nitrogen bond can be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flame-retardant additives are commercially available.
  • the organic compound containing a phosphorus-nitrogen bond is a phosphazene. A number of phosphazenes and their synthesis are described in H. R. Allcook, "Phosphorus-Nitrogen Compounds" Academic Press (1972), and J. E. Mark et al., "Inorganic Polymers” Prentice-Hall International, Inc. (1992).
  • the phosphorus -containing flame retardant comprises a poly(phosphonate) homopolymer, a poly(phosphonate-carbonate), resorcinol diphosphate, bisphenol A bis(diphenyl phosphate), triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl phosphate, phenoxyphosphazene, or a combination comprising at least one of the foregoing.
  • the phosphorus-containing flame retardant is an aryl phosphate having a molecular weight of about 350 to 1000 Daltons.
  • the amount of phosphorous-containing flame retardant present in the solution is an amount at least sufficient to provide a powder that can be used to manufacture an article having a UL94 V-2 rating, more preferable a V-l rating and most preferably aV-0 rating.
  • the amount can vary with the type of polycarbonate and with the efficiency of the particular flame retardant.
  • the amount of the phosphorous -containing flame retardant in the solution can be from 0.1 to 50 wt%, or from 5 to 15 wt%, each based on the total weight of the polycarbonate.
  • the amount of the phosphorous-containing flame retardant in the partially crystalline polycarbonate powder product can be from 0.1 to 40 wt%, or from 5 to 20 wt%, each based on the total weight of the partially crystalline polycarbonate powder/phosphorous-containing flame retardant product.
  • additives can be included in the solution (and the partially crystalline polycarbonate powder), for example those ordinarily incorporated into polycarbonate compositions, with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the powder or the articles formed from the powder, such as flame retardancy.
  • Such additives can be mixed into the solution before, during, or after the addition of the polycarbonate and the flame retardant.
  • Possible additives include impact modifiers, fillers, non-oxidants, heat stabilizers, light stabilizers, ultraviolet light (UV) absorbers (such as benzotriazoles), plasticizers, lubricants, mold release agents, antistatic agents, colorants, blowing agents, and radiation stabilizers.
  • a combination of additives can be used, for example, an antioxidant, a UV absorber, and a mold release agent.
  • the total amount of additives can be from 0.1 to 5.0 wt%, based on the total weight of the polycarbonate.
  • the phosphorous-containing flame retardant can have a high percentage of particles having a particle size of less than 150 micrometers, as well as a relatively narrow particle size distribution.
  • the partially crystalline polycarbonate powder has a D50 of less than 150 ⁇ , or a D85 particle size of less than 150 micrometers, or a D90 particle size of less than 150 micrometers.
  • a partially crystalline polycarbonate powder in which 100% of the particles (D100) have a size of less than 150 micrometers can also be produced by this method.
  • D50 refers to the particle diameter of the powder where 50 volume percent (vol%) of the particles in the total distribution of the referenced sample have the noted particle diameter or smaller.
  • a D85 refers to the particle diameter of the powder where 85 vol% of the particles in the total distribution of the referenced sample have the noted particle diameter or smaller
  • D90 refers to the particle diameter of the powder where 95 vol% of the particles in the total distribution of the referenced sample have the noted particle diameter or smaller
  • DlOO refers to the particle diameter of the powder where 100 vol% of the particles in the total distribution of the referenced sample have the noted particle diameter or smaller.
  • Particle sizes can be measured by any suitable methods known in the art to measure particle size by diameter.
  • the particle size is determined by laser diffraction as is known in the art.
  • particle size can be determined using a diffractometer such as the Mastersizer 3000 from Malvern.
  • the product partially crystalline polycarbonate powder can have an average particle diameter of less than or equal to 100 ⁇ .
  • the partially crystalline polycarbonate powder can have an average particle diameter of 10 ⁇ to 100 ⁇ .
  • the term "average particle diameter" refers to the average (mean) size of the particles as measured by diameter.
  • the product partially crystalline polycarbonate powder has a percent crystallinity greater than that of the starting amorphous polycarbonate.
  • the starting crystallinity is of the polycarbonate polymer is 0% (i.e., the polymer is 100% amorphous). The percentage is based upon the total weight of the partially crystalline polycarbonate powder.
  • the partially crystalline polycarbonate powder can have a percent crystallinity of at least 3%, for example 10% to 45%, or at least 20%, for example 20% to 40%, or at least 25%, for example 25% to 35%. In some embodiments the partially crystalline polycarbonate powder can have 20% to 30% crystallinity.
  • pellet bed fusing or “powder bed fusion” is used herein to mean processes wherein the polycarbonate is selectively sintered or melted and fused, layer-by-layer to provide a 3-D object. Sintering can result in objects having a density of less than about 90% of the density of the solid powder composition, whereas melting can provide objects having a density of 90% to 100% of the solid powder composition.
  • Use of crystalline polycarbonate as herein disclosed can facilitate melting such that densities close to achieved by injection molded can be attained.
  • Powder bed fusing or powder bed fusion further includes all laser sintering and all selective laser sintering processes as well as other powder bed fusing technologies as defined by ASTM F2792-12a.
  • sintering of the powder composition can be accomplished via application of electromagnetic radiation other than that produced by a laser, with the selectivity of the sintering achieved, for example, through selective application of inhibitors, absorbers, susceptors, or the electromagnetic radiation (e.g., through use of masks or directed laser beams).
  • Any other suitable source of electromagnetic radiation can be used, including, for example, infrared radiation sources, microwave generators, lasers, radiative heaters, lamps, or a combination thereof.
  • SMS selective mask sintering
  • U.S. Pat. No. 6,531,086 which describes an SMS machine in which a shielding mask is used to selectively block infrared radiation, resulting in the selective irradiation of a portion of a powder layer.
  • the powder composition can include one or more heat absorbers or dark-colored materials (e.g., carbon black, carbon nanotubes, or carbon fibers).
  • the partially crystalline polycarbonate powder containing a phosphorous -containing flame retardant can be used as the sole component in the powder composition and applied directly in a powder bed fusing step.
  • the powder can also be combined with other optional components, as described below, such as a flow agent. Any optional component is present in a sufficient amount to perform its intended function without significantly adversely affecting the powder composition or an article prepared therefrom. Any optional components can have an average particle diameter which falls within the range of the average particle diameters of the crystalline polycarbonate powder or flow agent. If needed, an optional component can be milled to the desired particle size and/or particle size distribution. It is not necessary for each optional component to melt during the laser sintering process, but use of optional components compatible with the partially crystalline polycarbonate can provide a strong and durable article of manufacture by the powder bed fusing process.
  • the optional components can be particulate materials and include organic and inorganic materials such as fillers, flow agents, coloring agents (dyes or pigments, such as carbon black), reinforcing agents, toners, extenders, fillers, lubricants, anticorrosion agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, organic solvents, surfactants, additional flame retardants, non-static agents, plasticizers, or a
  • the polymer content in the powder composition used in the powder bed fusing comprises from 50 to 100 wt% of the crystalline polycarbonate, based on the total weight of all polymeric materials in the powder composition.
  • Combinations of the optional components can be used, for example a flow agent, and a second polymer.
  • Each individual optional component can be present in the powder composition in an amount of 0.01 to 30 wt%, based on the total weight of the powder composition.
  • the total amount of all optional components in the powder composition can be from 0 up to 30 wt%, based on the total weight of the powder composition.
  • the optional component can be a reinforcing agent that imparts additional strength to the article of manufacture.
  • the reinforcing agent include glass fibers, carbon fibers, talc, clay, wollastonite, glass beads, or a combination comprising at least one of the foregoing reinforcing agents.
  • the optional component can be a flow agent.
  • the optional flow agent can be a particulate inorganic material having a median particle size of 10 ⁇ or less, or 100 nm or less.
  • the flow agent can be a hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titania, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, or magnesium silicate.
  • a particularly useful flow agent is fumed silica.
  • the flow agent can be present in an amount sufficient to allow the polycarbonate to flow and level on the build surface of the laser sintering device.
  • the powder composition can include a particulate flow agent in an amount of 0.01 to 5 wt%, or 0.05 to 1 wt%, or 0.1 to 0.25 wt%, each based on the total weight of the powder composition.
  • powder bed fused (e.g., laser sintered) articles can be produced from the powder compositions using any suitable powder bed fusing processes including laser sintering processes.
  • These articles can include a plurality of overlying and adherent sintered layers that include a polymeric matrix which, in some embodiments, have reinforcement particles dispersed throughout the polymeric matrix.
  • Laser sintering processes are sufficiently well known, and are based on the selective sintering of polymer particles, where layers of polymer particles are briefly exposed to laser light and the polymer particles exposed to the laser light are thus bonded to one another. Successive sintering of layers of polymer particles produces three-dimensional objects. Details concerning the selective laser sintering process are found, by way of example, in the specifications U.S.
  • the powder described herein can also be used in other rapid prototyping or rapid manufacturing processing of the prior art, in particular in those described above.
  • the powder can in particular be used for producing moldings from powders via the SLS
  • a plurality of layers is formed in a preset pattern by an additive manufacturing process.
  • "Plurality" as used in the context of additive manufacturing includes 5 or more layers, or 20 or more layers.
  • the maximum number of layers can vary greatly, determined, for example, by considerations such as the size of the article being manufactured, the technique used, the capabilities of the equipment used, and the level of detail desired in the final article. For example, 5 to 100,000 layers can be formed, or 20 to 50,000 layers can be formed, or 50 to 50,000 layers can be formed.
  • layer is a term of convenience that includes any shape, regular or irregular, having at least a predetermined thickness.
  • the size and configuration two dimensions are predetermined, and on some embodiments, the size and shape of all three-dimensions of the layer is predetermined.
  • the thickness of each layer can vary widely depending on the additive manufacturing method. In some embodiments the thickness of each layer as formed differs from a previous or subsequent layer. In some embodiments, the thickness of each layer is the same. In some embodiments the thickness of each layer as formed is 0.1 millimeters (mm) to 1 mm.
  • the preset pattern can be determined from a three-dimensional digital representation of the desired article as is known in the art and described in further detail below.
  • the fused layers of powder bed fused articles can be of any thickness suitable for selective laser sintered processing.
  • the individual layers can be each, on average, preferably at least 50 micrometers ( ⁇ ) thick, more preferably at least 80 ⁇ thick, and even more preferably at least 100 ⁇ thick.
  • the plurality of sintered layers are each, on average, preferably less than 500 ⁇ thick, more preferably less than 300 ⁇ thick, and even more preferably less than 200 ⁇ thick.
  • the individual layers for some embodiments can be 50 to 500 ⁇ , 80 to 300 ⁇ , or 100 to 200 ⁇ thick.
  • Three-dimensional articles produced from the powder compositions using a layer-by-layer powder bed fusing processes other than selective laser sintering can have layer thicknesses that are the same or different from those described above.
  • the partially crystalline polycarbonate powder with phosphorous-containing flame retardant is used to manufacture a unidirectional fiber reinforced polycarbonate composite.
  • the partially crystalline nature of the polycarbonate powder allows ease of processing, and results in lower required melting energy versus the melting of corresponding amorphous polycarbonates.
  • This method can include providing an aqueous dispersion of a powder composition comprising the partially crystalline polycarbonate powder containing the phosphorous-containing flame retardant composition; passing a continuous fiber tape through said aqueous dispersion to form an unidirectional fiber reinforced polycarbonate composite; drying the unidirectional fiber reinforced polycarbonate composite; and optionally further processing the dried composite form under high temperature and pressure conditions to melt the polymer to achieve better impregnation of unidirectional fiber by the polymer.
  • the continuous fiber tape is a continuous carbon tape.
  • Resorcinol diphenyl phosphate (RDP) Bisphenol A diphenyl phosphate (BPADP) (P content: 10.8%) P content: 9% FRX Homopolymer
  • PC polycarbonate
  • acetone crystallizing anti-solvent
  • Phosphorous can be incorporated within the PC particles following the process flow diagram shown in FIG. 1.
  • all phosphorous appeared to be lost during the step of isolating the precipitated by decanting the acetone/DCM solvent/non- solvent combination.
  • the process was modified to evaporate this acetone/DCM combination instead, which then successfully demonstrated retention of phosphorous on the PC particles. See additional experiments below.
  • the proposed method allows successful incorporation of non- halogenated flame retardant additives (fluid/pellet form) within polycarbonate powders, without affecting its percent crystallinity or free flowing characteristics.
  • Control PC no FR
  • PC with RDP and BPADP show resulting powders to have a mono-modal distribution.
  • the particle size increases as a function of the viscosity of the medium.
  • PC with FRX-PC showed a bi-modal distribution, as can be seen from the particle size distribution figures below.
  • Table 2 shows the different levels of particle sizes measured from the experimental samples.
  • Table 3 Elemental breakdown of various PC partic es as estimated from EDX measurements.
  • the method enables production of flame retardant PC powders through a single process approach based on solvent/non- solvent process.
  • This invention addresses a critical need to have fine PC powder particles (compared to current state of the art) to produce high quality continuous fiber reinforced PC tapes with flame retardant properties.
  • Particle Size Distribution The volume based particle size distribution was measured in methanol (shown in Table 7) using laser diffraction technology (Mastersizer 20000 from Malvern) and reported as D10, D50, and D90 values. A small amount of the DCM/MEK suspension was taken and diluted with acetone. The resulting slurry was added to the Malvern reservoir filled with methanol to study the particle size distribution.
  • DSC Differential Scanning Calorimetry
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry
  • the phosphorus concentration (%P) in the diluted sample solutions was quantified using a multi-element calibration standard set from Inorganic Ventures using an Agilent 7500cx ICP-MS system and converted to RDP concentration (%RDP) based on a 10.9 wt% phosphorus content of RDP.
  • the same polycarbonate with a molecular weight of 21,800 g/mol was used in these experiments as used above in the previous Examples.
  • Table 7 Property data for FR-PC powders produced from varying initial RDP content, using filtration to isolate the powders.
  • FIG. 3 shows a graph comparing the starting and final amounts of RDP measured along with a representative 'ideal' situation assuming how the data plot might look like if 100% of the RDP was retained in the final FR-PC powder.
  • RDP is also desirable due to its ability to reduce the Tg of polycarbonates.
  • FIG. 2 A more effective embodiment is shown in FIG. 2, replacing the filtration step for an evaporation step, which forces a much higher amount of RDP to be retained in the remaining FR-PC powder.
  • Table 8 shows the results for formulations with 5wt%, 10 wt% and 20 wt% RDP in the starting FR-PC mixture (see Table 6), where the DCM/MEK suspensions were transferred to a round-bottom flask and put on a rotary evaporator with the temperature of the water bath set at 40°C. The pressure was stepwise reduced to 500 mbar and kept at this pressure for an additional 60 minutes, to remove the solvent (DCM) and non- solvent (MEK). The remaining FR-PC powder was dried in a vacuum oven (50 mbar) overnight at 100°C. The same polycarbonate with a molecular weight of 21,800 g/mol was used in these experiments as used above in the previous Examples.
  • Table 8 Property data for FR-PC powders produced from varying initial RDP content, using evaporation to isolate the powders.
  • a method of preparing a partially crystalline polycarbonate powder containing a phosphorous -containing flame retardant comprising: dissolving an amorphous polycarbonate and a phosphorous -containing flame retardant in a halogenated alkane solvent to form a solution; combining the solution with a crystallizing non-solvent that is miscible with the halogenated alkane solvent; and mixing the combined solution and
  • Aspect 2 The method of Aspect 1 wherein the phosphorous -containing flame retardant is added to the solvent before the polycarbonate is dissolved, or together with the polycarbonate, before the addition of the crystallizing non-solvent.
  • Aspect 3 The method of Aspect 1 wherein the phosphorous-containing flame retardant is added after dissolving the amorphous polycarbonate solution and before the addition of the crystallizing non-solvent.
  • Aspect 4 The method of any of Aspects 1-3, further comprising: removing the halogenated alkane solvent and the crystallizing non-solvent from the precipitate; and optionally, drying the precipitate.
  • Aspect 5 The method of Embodiment 4, wherein the removing the halogenated alkane solvent and the crystallizing non- solvent from the precipitate comprises filtering the precipitate.
  • Aspect 6 The method of Aspect 4, wherein the removing the halogenated alkane solvent and the crystallizing non- solvent from the precipitate comprises at least partially evaporating the solvents from the precipitate.
  • Aspect 7 The method of any of Aspects 1-6, wherein the halogenated alkane solvent comprises dichloromethane, chloroform, methylene chloride, or a combination comprising at least one of the foregoing.
  • Aspect 8 The method of any of Aspects 1-7, wherein the crystallizing non- solvent comprises acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, or a combination comprising at least one of the foregoing.
  • Aspect 9 The method of any of Aspects 1-8, wherein the high shear mixing comprises mixing at a speed of 2,000 to 50,000 rpm.
  • Aspect 10 The method of any of Aspects 1-9, wherein the amorphous polycarbonate is a polycarbonate homopolymer, a poly(ester-carbonate), a poly(siloxane- carbonate), a poly(ester-siloxane-carbonate), or a combination comprising at least one of the foregoing.
  • Aspect 11 The method of any of Aspectsl-10, wherein the phosphorus- containing flame retardant comprises a poly(phosphonate) homopolymer, a poly(phosphonate- carbonate), resorcinol diphosphate, bisphenol A bis(diphenyl phosphate), triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl phosphate, phenoxyphosphazene, or a combination comprising at least one of the foregoing.
  • the phosphorus- containing flame retardant comprises a poly(phosphonate) homopolymer, a poly(phosphonate- carbonate), resorcinol diphosphate, bisphenol A bis(diphenyl phosphate), triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl phosphate, phenoxyphosphazene, or a combination comprising at least one of the foregoing.
  • Aspect 12 The method of any of Aspects 1-11, wherein the halogenated alkane solvent is dichloromethane, wherein the crystallizing non-solvent is methyl ethyl ketone, and the removing the halogenated alkane solvent and the crystallizing non-solvent from the precipitate comprises at least partially evaporating the solvents from the precipitate.
  • Aspect 13 A partially crystalline polycarbonate powder comprising a phosphorous-containing flame retardant prepared by the method of any of Aspect s 1-12.
  • Aspect 14 The partially crystalline polycarbonate powder of claim 13, wherein the polycarbonate is a polycarbonate homopolymer, a poly(carbonate-siloxane), or a
  • the phosphorus-containing flame retardant is a poly(phosphonate) homopolymer, a poly(phosphonate-carbonate), resorcinol diphosphate, bisphenol A bis(diphenyl phosphate), triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl phosphate, phenoxyphosphazene, or a combination comprising at least one of the foregoing; and wherein the amount of the phosphorous-containing flame retardant in the partially crystalline polycarbonate powder product is from 0.1 to 40 wt%, based on the total weight of the partially crystalline polycarbonate powder/phosphorous-containing flame retardant product.
  • a method of preparing a three-dimensional article comprising: providing a powder composition comprising the partially crystalline polycarbonate powder containing phosphorous-containing flame retardant of any of Aspects 13-14; and powder bed fusing the powder composition to form a three-dimensional article.
  • Aspect 16 The method of Aspect 15, wherein the powder bed fusing comprises selective laser sintering.
  • Aspect 17 A three-dimensional article made by the method of any of Aspects 15-16, comprising a plurality of fused layers, preferably comprising at least five fused layers.
  • a method of preparing a unidirectional fiber reinforced polycarbonate composite comprising: providing an aqueous dispersion of a powder composition comprising a partially crystalline polycarbonate powder containing a phosphorous-containing flame retardant of any of Aspects 13-14; passing a continuous fiber tape through said aqueous dispersion to form an unidirectional fiber reinforced polycarbonate composite; and drying the unidirectional fiber reinforced polycarbonate composite.
  • Aspect 19 The method of Aspect 19, wherein the continuous fiber tape is a continuous carbon tape.
  • Aspect 20 The method of Aspect 19, wherein the Tg of the polycarbonate in the unidirectional fiber reinforced polycarbonate composite is suppressed 3 to 50 degrees C by the presence of the phosphorous -containing flame retardant.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
  • alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CH 2 ) 3 - )).
  • Cycloalkylene means a divalent cyclic alkylene group, -C n H 2n - x , wherein x is the number of hydrogens replaced by cyclization(s).
  • Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
  • Arylene means a divalent aryl group.
  • Alkylarylene means an arylene group substituted with an alkyl group.
  • Arylalkylene means an alkylene group substituted with an aryl group (e.g., benzyl).
  • halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.

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Abstract

L'invention concerne un procédé de préparation d'une poudre de polycarbonate partiellement cristalline contenant un retardateur de flamme contenant du phosphore, le procédé comprenant les étapes consistant à: dissoudre un polycarbonate amorphe et un retardateur de flamme contenant du phosphore dans un solvant alcane halogéné pour former une solution; combiner la solution avec un non solvant formant des cristaux qui est miscible avec le solvant alcane halogéné; et mélanger la solution combinée et le non solvant formant des cristaux dans des conditions de mélange à cisaillement élevé efficaces pour former un précipité de polycarbonate partiellement cristallin. L'invention porte également sur un article tridimensionnel obtenu par fusion sur lit de poudre d'une composition pulvérulente la comprenant et un procédé de production d'un composite de polycarbonate renforcé par des fibres unidirectionnelles comprenant l'imprégnation d'une bande de fibre continue avec une dispersion aqueuse de cette poudre.
PCT/US2018/052120 2017-09-22 2018-09-21 Procédé de production de poudre de polycarbonate semi-cristalline avec un retardateur de flamme ajouté pour la fusion de poudre et applications de composites WO2019060657A1 (fr)

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