EP3638842A1 - Dispersions polymères aqueuses, procédés de fabrication de telles dispersions polymères aqueuses et mèches de fibres ensimées - Google Patents

Dispersions polymères aqueuses, procédés de fabrication de telles dispersions polymères aqueuses et mèches de fibres ensimées

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Publication number
EP3638842A1
EP3638842A1 EP18772864.7A EP18772864A EP3638842A1 EP 3638842 A1 EP3638842 A1 EP 3638842A1 EP 18772864 A EP18772864 A EP 18772864A EP 3638842 A1 EP3638842 A1 EP 3638842A1
Authority
EP
European Patent Office
Prior art keywords
aqueous dispersion
sizing
carbon fiber
polycarbonate
fiber tow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18772864.7A
Other languages
German (de)
English (en)
Inventor
Haimanti DATTA
Jan Henk Kamps
Reema Sinha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHPP Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Priority claimed from PCT/IB2018/055795 external-priority patent/WO2019026008A1/fr
Publication of EP3638842A1 publication Critical patent/EP3638842A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D06M15/513—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/313—Unsaturated compounds containing phosphorus atoms, e.g. vinylphosphonium compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • This disclosure relates aqueous polymeric dispersions and to sized carbon fiber tows, and in particular to sized carbon fiber tows with a low concentration of volatile organic compounds (VOC), and methods for preparing the same.
  • VOC volatile organic compounds
  • Non-uniform particle sized dispersions can lead to poor surface coverage. Additionally, non-uniform appearance/finish can arise due to packing defects during film formation. This can lead to low throughput as well as poor performance of the material.
  • the powders can be formed in dispersions that can be used, for example, in sizing fibers and fiber strands.
  • Sized carbon fibers have enhanced inter-laminar shear strength (ILSS), resulting in improved fiber-matrix adhesion and thereby enhancing the desired properties of composites.
  • sized carbon fibers have improved processability by way of improved fiber bundle cohesion, spreadability, resistance to fuzz formation, fiber smoothness, abrasion resistance, and windability.
  • sizing of reinforcing fibers is a critical step for preparing commercial fiber-reinforced composites.
  • One key parameter for assessing the quality of sizing is the extent of sizing or the sizing content across a fiber.
  • a uniform sizing content provides the necessary quality of matrix- fiber adhesion, resulting in composites having improved properties.
  • matrix-fiber adhesion and wettability may be further improved by using a sizing agent of the same material as the matrix in which the sized carbon fiber is to be dispersed.
  • Polymer material such as polycarbonates resins is one such material, which meets the criteria and is extensively used in the consumer electronic industry inter alia due to its low weight, high optical transparency, and high impact strength. The possibility of using polycarbonate as a sizing agent has been explored in the past.
  • Polycarbonate based aqueous dispersion although desirable in sizing application, has some inherent drawbacks such as non-uniform resin particle size distribution resulting in improper sizing content on the reinforcing fibers.
  • Non-uniform particle sized dispersions can lead to poor surface coverage.
  • non-uniform appearance/finish can arise due to packing defects during film/sizing formation. This can lead to low throughput as well as poor performance of the composite product. Sizing application of fiber can necessitate significantly smaller particles/dispersions to ensure optimum impregnation and thermodynamic wet-out.
  • thermoplastics such as polyetherimide (PEI) as sizing agent on carbon fibers to obtain sizing, which is environmentally benign as well as uniform on the carbon fiber surface.
  • PEI polyetherimide
  • aqueous dispersion characteristics of PEI will be different from that of a polycarbonate dispersion on account of the different chemical functional/substituent groups present on the polymers leading to a different sizing extent on the carbon fiber surface.
  • aqueous dispersions Disclosed herein are aqueous dispersions, methods of making aqueous dispersions, articles comprising elements formed from aqueous dispersions, sized carbon fibers, and methods for making sized carbon fibers.
  • an aqueous dispersion can comprise: a plurality of particles each particle comprising a polycarbonate component, wherein individual particles have a D90 in a range of 300 nm to 4,000 nm; a plasticizer component; and a surfactant component.
  • a method of forming the aqueous dispersion can comprise: combining an organic phase and an aqueous phase to form a first solution, the organic phase comprising a polycarbonate component and a solvent component, the aqueous phase comprising water and a surfactant component; heating the first solution to evaporate the solvent component; and form a second solution; and combining a plasticizer component with the second solution to form the aqueous dispersion.
  • a sized carbon fiber tow can comprise: a polycarbonate sizing on a carbon fiber tow, wherein the polycarbonate sizing has a concentration of volatile organic compounds less than 10 ppm, preferably less than 5 ppm, or less than 2 ppm; and an average sizing content of at least 0.5 wt% of the carbon fiber tow with a coefficient of variation less than 15 , preferably less than 11%.
  • a method of preparing the sized carbon fiber tow can comprise: spreading the carbon fiber tow over a spreader unit at a throughput line speed of at least 0.3 meters/minute and forming spread carbon fibers; sizing the spread carbon fibers in a sizing bath containing an aqueous polycarbonate sizing dispersion and forming sized carbon fibers; and drying the sized carbon fibers to obtain the sized carbon fiber tow.
  • FIG. 1 is a flow chart of a method of preparing an aqueous dispersion, in accordance with various examples.
  • FIG. 2 is a schematic diagram showing the formation of the aqueous dispersion, in accordance with various examples.
  • FIG. 3 is a transmission electron microscopy image showing the aqueous dispersion, in accordance with various examples.
  • FIG. 4 is a graph showing the dynamic light scattering output of the aqueous dispersion, in accordance with various examples.
  • FIG. 5 is a Pareto chart showing the effect of various process parameters on the aqueous dispersion, in accordance with various examples.
  • FIG. 6 is a bar graph showing the minimum film formation temperature of the aqueous dispersion with different amounts of resorcinol diphenyl phosphates included therein, in accordance with various examples.
  • FIGs. 7A-7C are hot state tapping mode atomic force microscopy images showing the surface roughness of various films formed from the aqueous dispersion, accordance with various examples.
  • FIG. 8 is an illustration of the overall process flow diagram for carbon fiber sizing and its subsequent application in composites and woven fabrics.
  • FIG. 9 is a graphical representation of the lowering of coefficient of variation in sizing content based on the results from Example 3.
  • FIG. 10 is a graphical representation illustrating the lowering of VOC concentration in the sized carbon fiber tow based on the results of Example 3.
  • a potential solution to the problems described herein is to employ an aqueous dispersion that includes a polycarbonate component, a plasticizer component, and a surfactant component.
  • Aqueous dispersions can deliver stable, small particle sized dispersion (e.g., sub- micrometer scale, controllable by adjusting reagents used in making the aqueous dispersion) with uniform distribution (e.g., monomodal) of particles. This can allow the films, coatings, or powders formed from the aqueous dispersion to have better packing efficiency.
  • the plasticizer can impart a low minimum film formation temperature (MFFT) to the aqueous dispersion, which facilitates easy and substantially defect free film formation.
  • the aqueous dispersions can be quite stable and show substantially no phase separation. For example, no phase separation is observed for times ranging from one month to several years.
  • the aqueous dispersion can be used as a sizing composition in preparing a polycarbonate sized carbon fiber tow, having a low concentration of volatile organic compounds and a uniform sizing content across the carbon fiber tow.
  • the polycarbonate sized carbon fiber can have a concentration of VOC of less than 10 ppm with an average sizing content greater than 0.5 wt% of the carbon fiber tow.
  • the inventors surprisingly found that the sizing content of the carbon fiber tow, is uniform as represented by a coefficient of variation not greater than 15% of the average sizing content.
  • the patent also describes a method of preparing a polycarbonate sized carbon fiber tow using the aqueous polycarbonate dispersion.
  • the extent of uniformity of the sizing deposited on the carbon fiber tow is expressed as the coefficient of variation (CoV) of the sizing content across a predetermined length of the sized carbon fiber tow.
  • the predetermined length of the sized carbon fiber tow serves as a sample or representative length to characterize the sizing quality across the sized carbon fiber tow.
  • the predetermined length of the sized carbon fiber tow for sizing content measurement is at least 30 cm, but preferably less than about 100 cm. For example, the predetermined length can be 30 cm. It is observed that at predetermined lengths lower than 30 cm, the weight of the sized carbon fiber tow, is not sufficient to provide an accurate measurement. At predetermined lengths greater than 100 cm, the sizing measurement becomes difficult using the commercially available analytical instruments.
  • the coefficient of variation may be determined from the average sizing content and the standard deviation of the sizing content measured across the predetermined length of the carbon fiber tow. It will be apparent that the sizing content across a particular predetermined length of the sized carbon fiber tow will be lower for a uniformly sized carbon fiber tow as compared to a non-uniform sized carbon fiber tow.
  • the sizing content of the sized carbon fiber can be measured by ash test or solvent digestion technique (ASTM D2584) depending on the type of sizing agent used and can be calculated as shown below using Formula I.
  • Sizing content is the average sizing content of a carbon fiber measured using the formula:
  • wi weight of sized carbon fiber tow
  • wo weight of carbon fiber tow (unsized).
  • the sizing content of the sized carbon fiber tow is found to be optimum with an average sizing content of at least 0.5 wt of the carbon fiber tow.
  • the average sizing content of the sized carbon fiber tow is at a range of 0.6 wt to 3 wt , preferably at a range of 0.85 wt to 2.8 wt and most preferably at a range of 0.95 wt to 2.4 wt , of the carbon fiber tow.
  • the standard deviation may be calculated using the formula
  • Xi being the result of the i-th measurement of sizing content using Formula I and x a is the average sizing content across the predetermined length of the carbon fiber tow.
  • the coefficient of variation may be calculated using the formula:
  • x a is the average sizing content across the predetermined length of the carbon fiber tow and S is the standard deviation of the measured sizing content measured across the predetermined length of the carbon fiber tow.
  • the coefficient of variation (CoV) of the sizing content is found to be less than 15%, preferably less than 12%, and most preferably less than 11 %, when measured across a predetermined length of the carbon fiber tow.
  • the polycarbonate sized carbon fiber tow has low VOC content, is
  • the VOC concentration present in the sized carbon fiber tow is less than 10 ppm, preferably less than 5 ppm, more preferably less than 2 ppm and most preferably less than 1 ppm, as measured using a gas chromatographic technique.
  • the low VOC concentration of the sized carbon fiber tow is achieved by using an aqueous solvent for dispersing the polycarbonate sizing agent. The need of using
  • An aqueous dispersion can include a plurality of particles suspended and homogenously distributed in an aqueous medium along with a plasticizer and a surfactant.
  • the aqueous dispersion can be well suited for many purposes.
  • the aqueous dispersion can be used to form a film.
  • the film in turn, can be used to form a sizing on a material such as fiber or a textile.
  • the aqueous dispersion can also be disposed on a surface of a substrate to form a film thereon, which coats the surface.
  • the particles of the aqueous dispersion can be isolated and a powder of the particles can be formed from the isolated particles.
  • the aqueous dispersion can be centrifuged and the supernatant removed from the solid; or the aqueous dispersion can be filtered to provide a filtrate.
  • the solid or filtrate can be washed with deionized water, e.g., one or more times.
  • the washed solid or filtrate can be dried, e.g., under vacuum, to provide the particles.
  • the particles can include a polycarbonate component.
  • Each individual particle of the plurality of particles has substantially the same size and morphology thus, having a monomodal distribution with a narrow dispersion.
  • the aqueous suspension can include a second plurality of particles each having the same size and morphology, however, the size and morphology of the second plurality of particles can be different than the first plurality of particles, thus creating a bimodal distribution.
  • the particles can account for any suitable weight percent (wt%) of the aqueous dispersion.
  • the particles can range from 0.5 wt% of the aqueous dispersion to 90 wt% of the dispersion, 10 wt% to 80 wt , 20 wt% to 80 wt , 30 wt% to 70 wt , or 40 wt% to 60 wt% of the aqueous dispersion.
  • the particles can range from 0.5 wt% of the aqueous dispersion to 5 wt% of the aqueous dispersion, 1.5 wt% to 4 wt , 2 wt% to 3.8 wt , 2.1 wt% to 2.8 wt% of the aqueous dispersion.
  • concentration of the polycarbonate resin particles may be customized as desired.
  • the individual particles can include a polycarbonate component.
  • the polycarbonate component can account for any suitable weight percentage of each particle.
  • the polycarbonate component can range from 50 wt% to 100 wt% of each of the particles, 60 wt% to 100 wt , 70 wt% to 100 wt , 80 wt% to 100 wt , or from 90 wt% to 100 wt% of each of the particles.
  • Polycarbonates and their methods of manufacture are known in the art, being described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923.
  • Polycarbonates are generally manufactured from bisphenol compounds such as 2,2-bis(4- hydroxyphenyl) propane (“bisphenol-A” or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane , or 1,1 -bis(4-hydroxyphenyl)-3 , 3,5- trimethylcyclohexane (isophorone), or a combination comprising at least one of the foregoing bisphenol compounds can also be used.
  • bisphenol compounds such as 2,2-bis(4- hydroxyphenyl) propane (“bisphenol-A” or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclo
  • the polycarbonate is a homopolymer derived from BPA; a copolymer derived from BPA and another bisphenol or dihydroxy aromatic compound such as resorcinol; or a copolymer derived from BPA and optionally another bisphenol or dihydroxyaromatic compound, and further comprising non- carbonate units, for example aromatic ester units such as resorcinol terephthalate or isophthalate, aromatic-aliphatic ester units based on Ce-20 aliphatic diacids, polysiloxane units such as polydimethylsiloxane units, or a combination comprising at least one of the foregoing.
  • aromatic ester units such as resorcinol terephthalate or isophthalate
  • aromatic-aliphatic ester units based on Ce-20 aliphatic diacids polysiloxane units such as polydimethylsiloxane units, or a combination comprising at least one of the foregoing.
  • Polycarbonate as used herein means a polymer or copolymer having repeating structural carbonate units of Formula (I):
  • each R 1 group can be the same or different.
  • 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 h is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a CMO alkyl, a halogen-substituted Ci-io alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4.
  • a Ci-io hydrocarbyl group such as a CMO alkyl, a halogen-substituted Ci-io alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl
  • n is 0 to 4.
  • R a and R b are each independently a halogen, Ci-12 alkoxy, or Ci-12 alkyl, and 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
  • R a and R b are each a C 1 -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 Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-is 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 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-l-one), l ,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, and l ,l-bis(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • PPPBP 3,3-bis(4- hydroxyphenyl) phthalimidine
  • 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine also
  • the polycarbonate contains carbonate units (1) and non- carbonate units, for example ester units, polysiloxane units such as polydimethylsiloxane units, or a combination comprising at least one of the foregoing.
  • ester units can be aromatic ester units (e.g., resorcinol terephthalate or isophthalate), or aromatic-aliphatic esters, based on C6-20 aliphatic diacids.
  • the polycarbonate is a linear homopolymer containing bisphenol A carbonate units (B PA-PC), commercially available under the trade name LEXANTM from SABICTM; or a branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via interfacial polymerization, containing 3 mol l , l, l-tris(4-hydroxyphenyl)ethane (THPE) branching agent, commercially available under the trade name LEXANTM CFR from SABICTM.
  • B PA-PC bisphenol A carbonate units
  • LEXANTM branched, cyanophenol end-capped bisphenol A homopolycarbonate produced via interfacial polymerization, containing 3 mol l , l, l-tris(4-hydroxyphenyl)ethane (THPE) branching agent
  • a specific copolycarbonate includes bisphenol A and bulky bisphenol carbonate units, e.g., derived from bisphenols containing at least 12 carbon atoms, for example 12 to 60 carbon atoms or 20 to 40 carbon atoms. Examples of such copolycarbonates include
  • copolycarbonates comprising bisphenol A carbonate units and 2-phenyl-3,3'-bis(4- hydroxyphenyl) phthalimidine carbonate units
  • a BPA-PPPBP copolymer commercially available under the trade name LEXANTM XHT from SABICTM
  • a copolymer comprising bisphenol A carbonate units and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate units
  • DMX a BPA-DMBPC copolymer commercially available under the trade name
  • poly(aromatic ester- carbonate ⁇ comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(carbonate-ester)s (PCE) or poly(phthalate- carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units.
  • PCE poly(carbonate-ester)s
  • PPC poly(phthalate- carbonate)s
  • Another specific poly(ester-carbonate) comprises resorcinol isophthalate and terephthalate units and bisphenol A carbonate units, such as those commercially available under the trade name LEXANTM SLX from SABICTM.
  • the polycarbonate is a poly(carbonate-siloxane) copolymer comprising bisphenol A carbonate units and siloxane units, for example blocks containing 5 to 200 dimethylsiloxane units, such as those commercially available under the trade name LEXANTM EXL from SABICTM.
  • Other polycarbonates that can be used include poly(ester- siloxane-carbonate)s comprising bisphenol A carbonate units, isophthalate-terephthalate- bisphenol A ester units, and siloxane units, for example blocks containing 5 to 200
  • dimethylsiloxane units such as those commercially available under the trade name LEXANTM FST from SABICTM.
  • Poly(aliphatic ester-carbonate)s can be used, such as those comprising bisphenol A carbonate units and sebacic acid-bisphenol A ester units, such as those commercially available under the trade name LEXANTM HFD from SABICTM.
  • Combinations of polycarbonates with other polymers can be used, for example an alloy of bisphenol A polycarbonate with an ester such as poly(butylene terephthalate) or poly(ethylene terephthalate), each of which can be semicrystalline or amorphous.
  • Such combinations are commercially available under the trade name XENOYTM and XYLEXTM from SABICTM.
  • the size of the individual particles can be controlled.
  • the individual particles have a substantially spherical shape (as is illustrated in FIG. 3) as opposed to an elongated or irregular shape.
  • the individual particles have a generally smooth surface that is substantially free of features such as edges, corners, protrusions, cavities, or the like.
  • the individual particles can have a diameter in the micrometer or nanometer range. The diameter of the individual particles can be governed by the selection of the surfactant component in the aqueous dispersion.
  • particles can have a D90 in a range of 300 nm to 4000 nm, 300 nm to 400 nm, 400 nm to 3500 nm, 500 nm to 3000 nm, 600 nm to 2000 nm, 700 nm to 1000 nm, or 800 nm to 900 nm.
  • the particles can have a D 8 of 340 to 345nm, e.g., 342 nm.
  • the aqueous dispersion can include additional components beyond the polycarbonate component.
  • the aqueous dispersion can include a plasticizer (also referred to as coalescing) component.
  • the plasticizer affects the minimum film formation temperature (MFFT) of the aqueous dispersion by functioning as a coalescing aid to assist film formation.
  • MFFT minimum film formation temperature
  • the minimum film formation temperature is the lowest temperature at which the aqueous dispersion will uniformly coalesce when applied on a substrate as a thin film. At a higher temperature the sizing agent may be damaged under the heat and in addition make the overall process energy inefficient.
  • MFFT-Bar as specified by such standards as ASTM D 2354 and ISO 2115.
  • the design of a potential instrument for testing the MFFT is based on these standards.
  • the plasticizer component can also aid in decreasing the surface tension value of the aqueous dispersion. Depending on the choice of plasticizer, the wettability of the aqueous dispersion can be selectively increased or decreased. Surprisingly, inclusion of the plasticizer component, in the aqueous dispersion leads to substantially no phase separation in the aqueous dispersion.
  • the plasticizer component can account for any suitable weight percentage of the aqueous dispersion.
  • the plasticizer component can range from 1 wt% to 20 wt% of the aqueous dispersion, 3 wt% to 19 wt , 4 wt% to 18 wt , 5 wt% to 17 wt , 6 wt% to 16 wt , 7 wt% to 15 wt , 8 wt% to 14 wt , 9 wt% to 13 wt , or 10 wt% to 12 wt% of the total weight of the aqueous dispersion.
  • the plasticizer component can include one or more plasticizers. Any of the one or more plasticizers can account for any suitable weight percent of the plasticizer component. For example, when two or more plasticizers are present, a plasticizer can range from 50 wt% to 100 wt% of the plasticizer component, 60 wt% to 100 wt , 70 wt% to 100 wt , 80 wt% to 100 wt , or 90 wt% to 100 wt% of the plasticizer component.
  • the plasticizer of the plasticizer component can include one or more selected from esters, ethers, hydrocarbons, paraffins, sulphonamides, sulfonates, terephthalates, terpenes, and trimellitates.
  • ester-based plasticizers are esters of mono- or di-basic acids such as myristate esters, phthalate esters, adipate esters, phosphate esters, citrates, trimellitates, glutarates, and sebacate esters (e.g., dialkyl phthalates, such as dibutyl phthalate, diisoctyl phthalate, dibutyl adipate, dioctyl adipate; 2-ethylhexyl diphenyl diphosphate; t-butylphenyl diphenyl phosphate; butyl benzylphthalates; dibutoxyethoxy ethyl adipate;
  • dialkyl phthalates such as dibutyl phthalate, diisoctyl phthalate, dibutyl adipate, dioctyl adipate
  • 2-ethylhexyl diphenyl diphosphate t-butylphen
  • Phosphate ester plasticizers are commercially sold under the trade designation SANTICIZERTM from Monsanto; St. Louis, MO.
  • Glutarate plasticizers are commercially sold under the trade designation
  • ester-based plasticizers include aliphatic monoalkyl esters, aromatic monoalkyl esters, aliphatic polyalkyl esters, aromatic polyalkyl esters, polyalkyl esters of aliphatic alcohols, phosphonic polyalkyl esters, aliphatic poly(alkoxylated) esters, aromatic poly(alkoxylated) esters, poly(alkoxylated) ethers of aliphatic alcohols, and poly(alkoxylated) ethers of phenols.
  • the esters are derived from an alcohol or from a renewable source, such as 2-octanol, citronellol, dihydrocitronellol or from 2- alkyl alkanols.
  • the plasticizer can be further chosen from an aliphatic monoalkyl ester, an aromatic monoalkyl ester, an aliphatic polyalkyl ester, an aromatic polyalkyl ester, a polyalkyl ester of an aliphatic alcohol, a phosphonic polyalkyl ester, an aliphatic poly(alkoxylated) ester, an aromatic poly(alkoxylated) ester, a poly(alkoxylated) ether of an aliphatic alcohol, a poly(alkoxylated) ether of a phenol, or mixtures thereof.
  • plasticizers which can also have flame retardant features include, organophosphorous compounds such as organic phosphates (including trialkyl phosphates such as triethyl phosphate, tris(2-chloropropyl)phosphate, and triaryl phosphates such as triphenyl phosphate and diphenyl cresyl phosphate, resorcinol bis-diphenylphosphate, resorcinol diphosphate, and aryl phosphate), phosphites (including trialkyl phosphites, triaryl phosphites, and mixed alkyl-aryl phosphites), phosphonates (including diethyl ethyl
  • organophosphorous compounds such as organic phosphates (including trialkyl phosphates such as triethyl phosphate, tris(2-chloropropyl)phosphate, and triaryl phosphates such as triphenyl phosphate and diphenyl cresyl phosphate,
  • phosphonate dimethyl methyl phosphonate
  • polyphosphates including melamine
  • polyphosphate ammonium polyphosphates
  • polyphosphites polyphosphonates
  • phosphinates including aluminum tris(diethyl phosphinate); halogenated compounds such as chlorendic acid derivatives and chlorinated paraffins; organobromines, such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane, polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers (BCOs), brominated epoxy oligomers (BEOs), tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD); metal hydroxides such as magnesium hydroxide, aluminum hydroxide, cobalt hydroxide, and hydrates of the foregoing metal hydroxide; and combinations thereof.
  • organobromines such as decabromodiphenyl ether (
  • the plasticizer can also be a reactive type compound (including polyols which contain phosphorus groups, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phospha-phenanthrene-10-oxide, phosphorus- containing lactone-modified polyesters, ethylene glycol bis(diphenyl phosphate),
  • the plasticizer can affect the minimum film formation temperature of the aqueous dispersion.
  • the minimum film formation temperature is the lowest temperature at which the aqueous dispersion will uniformly coalesce when applied on a substrate as a film (e.g., a thin film).
  • An example of a suitable test for determining this temperature involves using a MFFT-Bar, as specified by such standards as ASTM D 2354 and ISO 2115. The design of a potential instrument for testing the MFFT is based on these standards.
  • the plasticizer can also decrease the surface tension value of the aqueous dispersion. Depending on the choice of plasticizer, the wettability of the aqueous dispersion can be selectively increased or decreased. Surprisingly, inclusion of the plasticizer in the aqueous dispersion leads to substantially no phase separation in the aqueous dispersion.
  • a minimum film formation temperature (MFFT) of the aqueous dispersion can be 100 °C to 180 °C, 115 °C to 175 °C, 120 °C to 170 °C, 125 °C to 165 °C, 130 °C to 160 °C, 135 °C to 155 °C, or 140 °C to 150 °C.
  • the plasticizer can allow for the minimum film formation temperature of the aqueous dispersion to be less than that of a corresponding aqueous dispersion that is free of the plasticizer component.
  • a minimum film formation temperature of the aqueous dispersion can range from 10 °C to 50 °C less than a corresponding aqueous dispersion that is free of the plasticizer component, from 15 °C to 45 °C, 20 °C to 40 °C, or 25 °C to 35 °C less.
  • the lower minimum film formation temperature of the aqueous dispersion can allow a film to be formed at comparatively lower temperature than the corresponding aqueous dispersion. This can allow for quicker and less costly film formation.
  • the aqueous dispersion can include additional components beyond the polycarbonate component and the plasticizer component.
  • the aqueous dispersion can include a surfactant component.
  • the surfactant component can be present in an amount of 1 wt to 20 wt of the aqueous dispersion, 5 wt to 15 wt , or 8 wt to 12 wt of the aqueous dispersion.
  • the surfactant component can include one or more surfactants.
  • one surfactant can be 50 wt to 100 wt of the surfactant component, 60 wt% to 100 wt , 70 wt% to 100 wt , 80 wt% to 100 wt , or 90 wt% to 100 wt of the surfactant component.
  • the surfactant(s) can be an anionic surfactant, cationic, or a non-ionic surfactant.
  • anionic surfactants include stearate sodium, dodecyl sulfate sodium, dodecyl benzene, sulfonate sodium, alginic acid sodium, gly colic acid, ethoxylate 4-tert butylphenyl ether, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate 4-nonylphenyl ether, poly(ethylene glycol) 4-nonylphenyl 3-sulfopropyl ether potassium salt, sodium dioctyl sulphosuccinate, ammonium lauryl sulfate, dioctyl sodium sulfosuccinate, perfluorobutane sulfonic acid, perfluorononanoic acid, perfluorooctane sulfonic acid, perfluflufluor
  • non-ionic surfactants examples include poly(ethylene glycol) -Woc&-poly(propylene glycol)-Woc&-poly(ethylene glycol), poly(ethylene glycol) sorbitan tetraoleate, polyethylene -Woc&-poly(ethylene glycol), sorbitan monopalmitate,
  • cationic surfactants include benzalkonium chloride, benzethonium chloride, 5-bromo-5-nitro-l,3-dioxane, cetrimonium bromide (cetyl trimethylammonium bromide), cetyl trimethylammonium chloride, dimethyldioctadecylammonium chloride, lauryl methyl gluceth-10 hydroxypropyl dimonium chloride, tetramethylammonium hydroxide, or mixtures thereof.
  • the class of surfactant can have an impact on the morphology of the particles.
  • One impact the surfactant has on the morphology is that the particles have a substantially spherical shape in a monomodal or bimodal distribution.
  • the diameter of each particle can additionally be controlled. For example, if the surfactant is anionic then the particles will be monomodal in distribution with a diameter in the nanometer range. Alternatively, if the surfactant is nonionic then the particles will be monomodal in distribution with a diameter in the micrometer range.
  • a mixture of anionic and nonionic surfactants in the aqueous dispersion can lead to a bimodal distribution of particles with a nanometer diameter and particles with a micrometer distribution. Although in this instance, the substantial majority (e.g., 98 vol ) of the particles will have a diameter in the nanometer range.
  • aqueous dispersion Various additional components and additives can be present in the aqueous dispersion.
  • a solvent such as dichloromethane, chloroform, demethylformamide, dimethyl sulfate, tetrahydrofuran, or mixtures thereof can be present in the aqueous dispersion.
  • the solvent is selected to dissolve the polymer to the desired degree as described below; to have a boiling point less than water under the process conditions of forming the particles; and to be sufficiently immiscible with water to form a solution with water.
  • Additional additive(s) that can be present in the aqueous dispersion include a particulate filler, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, an ultraviolet absorbing additive, a non-infrared absorbing additive, an infrared absorbing additive, a lubricant, a release agent, an antistatic agent, an anti-fog agent, an antimicrobial agent, a colorant, a laser marking additive, a surface effect additive, a radiation stabilizer, an anti-drip agent, a fragrance, a fiber, a flow promoter, or a mixture thereof.
  • suitable flow promoters include an unmodified fumed metal oxide, a hydrophobic fumed metal oxide, a hydrophilic fumed metal oxide, hydrated silica, amorphous alumina, glassy silica, glassy phosphate, glassy borate, glassy oxide, titania, talc, mica, kaolin, attapulgite, calcium silicate, magnesium silicate, or a mixture thereof.
  • One non-limiting benefit that can be realized with the instant aqueous dispersion is that when the polycarbonate component, surfactant component, and plasticizer component are present, in the disclosed amounts, the aqueous dispersion shows good stability.
  • dispersions which include 1 wt% to 20 wt% plasticizer
  • substantially no phase separation has been visually observed in dispersions for a period of time exceeding one month.
  • no visible phase separation occurs in aqueous dispersions having a particle size ranging from 300 nanometers to 4000 nanometers for a period of time of at least 5 days, for example, at least 15 days, at least 45 days, at least two months, at least 6 months, at least 8 months, at least 12 months, and even at least 18 months.
  • the aqueous dispersion can form a sizing, powder, a film, a coating, a tie layer, an adhesive, a composite unidirectional tape, or a three-dimensional printed article.
  • a tie layer formed from the aqueous dispersion bonds a metal to a fluoropolymer, a powder coating, or an epoxy-toughening coating.
  • the aqueous dispersion can be applied to a fiber such as glass fibers, carbon fibers, aramid fibers, polyethylene fibers, polyester fibers, polyamide fibers, ceramic fibers, basalt fibers, steel fibers, and/or the like.
  • a fiber such as glass fibers, carbon fibers, aramid fibers, polyethylene fibers, polyester fibers, polyamide fibers, ceramic fibers, basalt fibers, steel fibers, and/or the like.
  • Carbon fibers or fiber strands can be used.
  • the strand of fibers can include, e.g., between 250 and 610,000 fibers (e.g., IK, 3K, 6K, 12K, 24K, or larger strands can be used).
  • sizing is a process in which fibers are coated with a material in order to protect the fibers from damage (e.g., splitting) during processing and to enhance adhesion between the fibers and materials that are subsequently applied to the fibers.
  • sizing is performed at least by contacting fibers from a strand of fibers with the aqueous dispersion. Such contacting can be performed by immersing the fibers in the dispersion, cascading the dispersion onto the fibers, brushing the dispersion onto the fibers, or spraying the dispersion onto the fibers.
  • such fibers can be disposed around a spool (e.g., in the form of a strand) for later use in making fiber tapes or laminates.
  • a spool e.g., in the form of a strand
  • such fibers can be woven into textiles and/or fabrics thus the aqueous dispersion can be part of a woven.
  • FIG.1 illustrates a general process flow diagram for preparing sized carbon fiber tow.
  • the sizing process can be initiated by unspooling a spool of unsized carbon fiber tow, e.g., procured from a supplier.
  • a spool of unsized carbon fiber tow is unspooled over a bobbin prior to spreading the carbon fiber tow.
  • the carbon fiber tow may be used directly by integrating the sizing line with a pre-sizing treatment unit without winding or unspooling the carbon fibers separately (e.g., the fibers can be sized directly without having been wound on a spool).
  • the unsized surface-treated carbon fiber tow may have carbon fiber filament number from 1000 (IK) to 50,000 (50K) filaments.
  • the carbon fiber filaments may have a diameter in a range of about 1 micrometer ( ⁇ ) to about 12 ⁇ , preferably in the range of about 3 ⁇ to about 10 ⁇ , and most preferably in the range of about 5 ⁇ to about 8 ⁇ .
  • a carbon fiber tow having filament number of 12K may be used.
  • the carbon fiber filaments can be derived from polyacrylonitrile (PAN) although other sources such as pitch, rayon, polyesters, polyamides, may also be used as a source for the carbon fiber filaments.
  • the carbon fiber filaments may be optionally electrolytically surface-treated prior to commencing the sizing process as disclosed in the US patent 4,234,398. Surface treatment or surface
  • One of the ways of achieving an optimum level of sizing on carbon fibers is to spread the unspooled carbon fibers to an optimum level of spreadability prior to applying the sizing agent.
  • An optimum level of spreadability ensures excellent resin impregnation resulting in improved resistance to delamination and improved mechanical properties in composite products.
  • the carbon fiber tow after unspooling can be drawn towards a spreader unit at a specific throughput line speed to generate spread carbon fibers.
  • the spreading unit can comprise at least five rollers, preferably at least six rollers, and most preferably at least seven rollers, over which the spread carbon fibers are processed.
  • Carbon fiber path in the spreading unit can have a total wrapping angle of at least 500 degrees and preferably at least 506 degrees.
  • the sizing equipment can have a tension controlled creel system from which a carbon fiber tow is dispatched and passed over to the spreader unit for spreading the carbon fiber tow.
  • the sizing equipment tension may be kept at a range of about 0.5 Newtons (N) to about 5 N for drawing the carbon fibers.
  • the sizing equipment tension can be kept at IN.
  • the sizing process should to take place within a specific range of throughput line speed for ensuring excellent sizing content and process productivity.
  • the spreading and sizing of the carbon fibers can be carried out at a throughput line speed of at least 0.3 meter/minute, preferably a throughput line speed of 0.4 meters/minute to 2 meter/minute, and most preferably at 0.8 meter/minute to 1.2 meter/minute.
  • Spreadability of the carbon fiber may be calculated by using Formula V.
  • the spreadability value of the carbon fibers when measured in accordance with Formula V is at least 150%, preferably in a range of 155% to 220%, and most preferably in a range of 178% to 202%.
  • Sa width of the unsized carbon fiber before entering the spreader unit.
  • the spread carbon fibers from the spreader unit can be drawn to a sizing bath containing the aqueous polymer dispersion (e.g., the aqueous polycarbonate sizing dispersion), for sizing the spread carbon fibers to form sized carbon fibers.
  • the dispersion can be maintained at an ambient room temperature.
  • the sizing can be carried out at a throughput line speed of at least 0.3 meter/minute, preferably at 0.4 meter/minute to 2 meter/minute, and most preferably at 0.8 meter/minute to 1.2 meter/minute.
  • the sized carbon fibers obtained from the sizing bath may be subsequently passed through a nip roller to squeeze out any excess aqueous dispersion on the carbon fiber surface before drying the fibers (e.g., in an oven) to obtain the sized carbon fiber tow. It has been observed that the drying of the sized carbon fibers should to be conducted at a raised temperature. At too low a temperature, the drying is ineffective while at very high temperature the sizing may get degraded.
  • the oven used for drying can be maintained at a temperature range of 150°C to 300°C and preferably in a range of 200°C to 270 °C, and most preferably in a range of 200 °C to 270 °C.
  • the sized carbon fiber tow may be subsequently wound on a spool, e.g., by a take-up winder, to be transported to a different location for further processing.
  • the sized carbon fiber tow can be directly passed to a production line for composite
  • the aqueous dispersion can be formed through various methods.
  • An example of a method of forming the aqueous dispersion includes combining an organic phase and an aqueous phase to form an emulsification composition.
  • the organic phase includes the polycarbonate component and the solvent component.
  • the aqueous phase includes water and the surfactant component.
  • the organic phase or the aqueous phase can include other components such as plasticizers or other additives.
  • the organic phase and the aqueous phase are added slowly to each other (e.g., drop-wise). Once the organic phase and aqueous phase are combined, the solution is formed.
  • the solution is formed at this stage with a homogenizer.
  • the homogenizer is able to mix the emulsification composition under high shear, e.g., ranging from 7,000 to 30,000 rpm or from 15,000 to 25,000 rpm.
  • the homogenizer operates for a time ranging from 2 to 40 minutes or from 8 to 30 minutes.
  • Once the solution is formed it is heated to a temperature sufficient to remove the solvent. The solvent then evaporates leaving the aqueous dispersion of particles, surfactant, plasticizer, and other optional additives.
  • AOT 70 PG (Sodium dioctyl sulphosuccinate in
  • TWEEN-80 Polyoxyethylenesorbitan monooleate
  • Tween 15-S-9 a secondary alcohol ethoxylate
  • Cremophor 25 (a ceteareth-25)
  • TMN-10 (a branched secondary alcohol ethoxylate)
  • Triton X-45 an octylphenol ethoxylate
  • TNP-40 (a nonylphenol ethoxylate)
  • RDP Resorcinol Diphenyl Phosphate
  • Dispersion-I was then transferred dropwise to a receiving vessel containing the surfactant/water mixture at 5 wt% surfactant with respect to the polymer concentration and maintained at a temperature of 75 °C for 30 min. After complete transfer, the receiving vessel was held at -80 °C for 10 minutes (with continuous stirring) to remove most of the organic solvent, leading to final PC dispersion with trace amount of residual DCM (ppm level).
  • FIG. 1 is a flow chart of the process
  • FIG. 2 is a schematic diagram of a possible mechanism of forming the aqueous dispersion.
  • High shear mixing of PC polymer in solvent and de-ionized water with surfactant produces emulsion droplets dispersed in water.
  • the surfactant with polar and non-polar ends protects these emulsion droplets from coalescing.
  • Solution or Dispersion-I (before DCM removal) leads to the formation of droplets with wide distribution, and phase separation observed after 1 day.
  • DCM dissolved in the water is removed, while DCM from inside the droplets evaporates into the water. It has been observed that droplets with wide distribution throughout the dispersion are formed through this emulsification process.
  • PC dispersion morphology (particle size/shape/distribution etc.) developed by the method could be fine-tuned by changing recipe/process parameters.
  • the resultant product gives stable polycarbonate aqueous dispersions (no phase separation, monitored over > 1 month), with 100% conversion (no left over residue).
  • Particle size and distributions were controlled by changing choice of surfactant and their composition Table 1).
  • Anionic surfactant AOT 70 PG provides submicron sized particles in dispersion whereas nonionic TWEEN 80 leads to micron sized particles, both with monomodal particle size distributions.
  • a combination of the above two surfactants leads to bimodal distributions, with a combination of smaller (sub-micron sized) and bigger (micron sized) ones.
  • Equation 1 D is the translational diffusion coefficient, k is the Boltzmann constant, T is the temperature in degrees Celsius (°C), and ⁇ is the liquid viscosity
  • Aqueous dispersions were analyzed for visible phase separation. A solution was considered to show visible phase separation when the polycarbonate particles were agglomerated or a distinct aqueous and organic phase were present. Samples were stored at room temperature. As shown in Tables 3 and 4, samples including polycarbonate particles having a monomodal distribution of particles not exceeding 4000 nanometers in size showed no phase separation after 60 days of storage. In contrast, aqueous dispersions having a bimodal distribution of polycarbonate particle or polycarbonate particles exceeding a size of 4000 nanometers showed visible phase separation after 15 days of storage. 16PLAS0326-WO-PCT
  • Table 3 Phase separation of aqueous dispersions having polycarbonate particles with sizes less than 4000 nm.
  • Minimum film formation temperature gradient plate was used to analyze the effect of particle size on film formation behavior of aqueous PC dispersions.
  • MFFT Minimum film formation temperature gradient plate
  • PC with 15 wt% RDP shows film formation, along with lowering in surface roughness (0.06 micron to 0.012 micron) when heated at 130°C (FIG. 7C), indicating, in part, a homogenous distribution of the polycarbonates.
  • Example 2 Preparing Aqueous Polymer Dispersion
  • FIG. 8 is a flow chart of the overall sizing process.
  • Polycarbonate dispersions of concentrations of 3.5, 2.5, 2.1 and 1.6 wt% were prepared in accordance with Example 1.1.
  • Flame retardant additive resorcinol diphenyl phosphate (RDP) was identified as a coalescing aid for the PC dispersion, which was introduced to the aqueous polycarbonate dispersion so obtained.
  • the RDP added may be 15 wt% of the aqueous sizing dispersion.
  • Example 3 Sizing Process and characterization of sized carbon fiber tow
  • Example 3 demonstrates an embodiment of the present invention where polycarbonate sized carbon fiber tow are prepared using the aqueous polycarbonate dispersion prepared as described under Example 2. The example further demonstrates the superior sizing content uniformity across the carbon fiber tow in addition to the low VOC concentration.
  • Material used A fiber sizing line fabricated by Izumi International, USA was custom designed.
  • Process/Procedure The polycarbonate dispersions were prepared at concentrations of 3.5, 2.5, 2.1, 1.6 wt% as described under Example 2. A carbon fiber tow was unspooled over a bobbin and was subsequently spread using a spreader unit to generate spread carbon fibers at a line speed of 1 m/min. The spread carbon fibers were passed through a sizing bath containing the aqueous polycarbonate sizing dispersion at a line speed of 1 m/min and sized carbon fibers were obtained. The sizing dispersion was stirred continuously with a stirrer for homogenization during the experiment. The sized carbon fibers was then passed through heaters for drying to obtain the sized carbon fiber tow.
  • the sized carbon fibers may be passed to the nip roller where excess sizing solution was taken out.
  • the sized carbon fiber tow was subsequently wounded around winder to be utilized for making composite products.
  • Headspace Gas Chromatography method was used for quantifying dichloromethane (DCM) content in the sized carbon fiber tow.
  • the dichloromethane was quantified using Flame Ionization Detector (FID). The process was repeated for each set of control to prepare the sized carbon fiber tow for further analysis.
  • carbon fiber tow sized with the polycarbonate aqueous dispersions of the present invention containing plasticizer component RDP has a lower coefficient of variation of sizing content compared to the corresponding carbon fiber tow prepared with aqueous sizing dispersion of polycarbonate having no plasticizer component.
  • the coefficient of variation of sizing content of the sized carbon fiber tow developed in the present embodiment of the invention was at least 33% lower compared to the sizing content of carbon fiber tow prepared using conventional polycarbonate aqueous dispersion without RDP. Thus indicating more uniformity in the sizing content for carbon fiber tow developed.
  • sized carbon fiber tow of the present embodiment of the invention prepared with polycarbonate aqueous dispersion containing the RDP as plasticizer component has a significantly lower VOC content.
  • VOC concentration of the sized carbon fiber tow developed in the present embodiment of the invention was as at least 95% lower than polycarbonate sized carbon fiber tow prepared with conventional dispersion of polycarbonate in DCM.
  • Result from Example 3 as an embodiment of the present invention demonstrate that polycarbonate sized carbon fiber tow of the present invention has excellent uniformity in sizing content along with low VOC concentration compared to conventional polycarbonate sized carbon fiber tow.
  • FIG. 9 and FIG. 10 provides a graphical representation of the lowering of coefficient of variation and VOC concentration in the sized carbon fiber tow.
  • the sized carbon fiber tow, as shown, complies with the requirement of having low concentration of VOC with excellent sizing content with the desired uniformity in the sizing content.
  • 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.
  • the terms "a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise.
  • the term “or” is used to refer to a nonexclusive “or” unless otherwise indicated.
  • the acts can be carried out in any order without departing from the principles of the disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
  • substantially refers to a majority of, or mostly, as in at least 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least 99.999% or more, or 100%.
  • solvent refers to a liquid that can dissolve a solid, liquid, or gas.
  • solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
  • polymer refers to a molecule having at least one repeating unit and can include copolymers.
  • the polymers described herein can terminate in any suitable way.
  • the polymers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci-C2o)hydrocarbyl (e.g., (Ci-Cio)alkyl or (C6-C2o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -0-, substituted or unsubstituted -NH-, and -S-, a poly(substituted or unsubstituted (Ci- C2o)hydrocarbyloxy), and a poly(substituted or unsubstituted (Ci-C2o)hydrocarbylamino).
  • a suitable polymerization initiator e.g., a substituted or unsubstituted (Ci-C2o)hydrocarbyl (e.g., (Ci-Cio)alky
  • substituted refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.
  • functional group refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, CI, Br, and I); an oxygen atom.
  • Non- limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR, OC(0)N(R) 2 , CN, NO, N0 2 , ON0 2 , azido, CF 3 , OCF 3 , R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R) 2 , SR, SOR, S0 2 R, S0 2 N(R) 2 , SO3R, C(0)R, C(0)C(0)R, C(0)CH 2 C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R) 2 , OC(0)N(R) 2 , C(S)N(R) 2 , (CH 2 )o- 2 N(R)C(0)R, (CH 2 )o- 2 N(R)N(R) 2 , N(R)N(R)C(0)R, N
  • alkyl refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • alkyl encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl.
  • Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
  • aryl refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • aryl groups contain 6 to 14 carbons in the ring portions of the groups.
  • Aryl groups can be unsubstituted or substituted, as defined herein.
  • Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8 -positions thereof.
  • anionic surfactant refers to anionic surfactants and zwitterionic or amphoteric surfactants which have an attached group that is anionic at the pH of the composition, or a combination thereof.
  • emulsion refers to a heterogeneous system of at least two immiscible liquids.
  • suspension refers to a suspension including solid particles.
  • bin means a bundle of carbon fibers comprising several thousand individual carbon fiber filaments bundled together in the form of a spool, which may be transported and handled for further processing.
  • throughput line speed means the speed at which the bobbins or spool or rollers, are rotated or operated at for drawing the carbon fiber filaments for sizing or spreading.
  • plasticizer means a compound, which helps in coalescing the polymer particles of the sizing composition to form a uniform sizing on the reinforcing carbon fiber and helps in reducing the minimum film forming temperature (MFFT) to form the sizing.
  • MFFT minimum film forming temperature
  • Minimum Film Forming Temperature is the temperature required to uniformly coalesce a sizing agent on the carbon fiber surface.
  • the term "drapability” or “drape” means flexibility or the bending ability of the sized fiber over a bobbin or a roller.
  • carbon fiber tow means a bundle of carbon fiber filaments without sizing.
  • sized carbon fiber means a bundle of carbon fiber filaments having polymeric coating on the surface of carbon fibers after dip-coating the carbon fiber in a sizing bath followed by drying.
  • sizing content means the extent of sizing or the amount of sizing or coating deposited on the carbon fiber tow surface expressed as a percentage weight of the unsized carbon fiber tow.
  • volatile organic compounds or "VOC” means organic solvents having low boiling point preferably lower than that of water and generally used for dissolving polymer resins.
  • substantially free of volatile organic compounds means that the concentration of volatile organic compounds is less than 10 ppm.
  • bobbin or "spool” means individual package comprising a carbon fiber roving which, is wound on to a core /support.
  • wrapping angle means the distance in degrees that the tensioned carbon fiber contacts the roller pins.
  • ppm means concentration of a substance expressed as parts per million by weight or the concentration of one part of a substance out of a million part of the total system in which the substance is present.
  • Aspect 1 provides an aqueous dispersion comprising: a plurality of particles each particle comprising a polycarbonate component, wherein individual particles have a D90 in a range of 300 nm to 4000 nm; a plasticizer component; and a surfactant component.
  • Aspect 2 provides the aqueous dispersion of Aspect 1, wherein the particles range from 5 wt% of the aqueous dispersion to 90 wt% of the dispersion.
  • Aspect 3 provides the aqueous dispersion according to any one of Aspects 1-2, wherein the particles range from 20 wt% of the aqueous dispersion to 80 wt% of the dispersion.
  • Aspect 4 provides the aqueous dispersion according to any one of Aspects 1-3, wherein the polycarbonate component ranges from 50 wt% to 100 wt% of each of the particles.
  • Aspect 5 provides the aqueous dispersion according to any one of Aspects 1-4, wherein the polycarbonate component ranges from 90 wt% to 100 wt% of each of the particles.
  • Aspect 6 provides the aqueous dispersion according to any one of Aspects 1-5, wherein the polycarbonate component comprises one or more polycarbonates, wherein the polycarbonates are the same or different polycarbonates.
  • Aspect 7 provides the aqueous dispersion of any of the preceding Aspects, wherein the polycarbonate component comprises at least one a linear homopolycarbonate, a branched, cyanophenol end-capped homopolycarbonate, a copolycarbonate comprising bisphenol A carbonate units and bisphenol carbonate units comprising 12 to 60 carbon atoms, a poly(aromatic ester-carbonate), poly(carbonate-siloxane), a poly(ester-siloxane-carbonate), and a poly(aliphatic ester-carbonate).
  • the polycarbonate component comprises at least one a linear homopolycarbonate, a branched, cyanophenol end-capped homopolycarbonate, a copolycarbonate comprising bisphenol A carbonate units and bisphenol carbonate units comprising 12 to 60 carbon atoms, a poly(aromatic ester-carbonate), poly(carbonate-siloxane), a poly(ester-siloxane-carbon
  • Aspect 8 provides the aqueous dispersion of Aspect 7, wherein the polycarbonate includes a repeating unit chosen from resorcinol, 2,2-bis(4-hydroxyphenyl) propane, 3,3-bis(4- hydroxyphenyl) phthalimidine, 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine, 3,3-bis(4- hydroxyphenyl)-2-phenylisoindolin- 1 -one), 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol), or mixtures thereof.
  • the polycarbonate includes a repeating unit chosen from resorcinol, 2,2-bis(4-hydroxyphenyl) propane, 3,3-bis(4- hydroxyphenyl) phthalimidine, 2-phenyl-3,3'-bis(4-hydroxypheny
  • Aspect 9 provides the aqueous dispersion of any of the preceding aspects, wherein the polycarbonate component comprises a polycarbonate copolymer.
  • Aspect 10 provides the aqueous dispersion of Aspect 9, wherein the polycarbonate is chosen from a copolymer comprising repeating units derived from bisphenol A carbonate units and 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine carbonate units, a copolymer comprising repeating units of bisphenol A carbonate units and l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane carbonate units a copolymer comprising bisphenol A carbonate units and l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5- trimethylcyclohexane isophorone bisphenol carbonate units copolymer comprising repeating units chosen from bisphenol A carbonate units and siloxane units.
  • the polycarbonate is chosen from a copolymer comprising repeating units derived from bisphenol A carbonate units and 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine carbonate units, a
  • Aspect 11 provides the aqueous dispersion of Aspect 10, wherein the repeating units of the polycarbonate copolymer are each independently in random, block, or alternating configuration.
  • Aspect 12 provides the aqueous dispersion according to any one of the preceding aspects, wherein the individual particles of the plurality of particles have a D90 in a range of 300 nm to 4000 nm, preferably a D90 in a range of 300 nm to 1000 nm, or a range of 300 nm to 600 nm, preferably the particles have a D 8 of 340 nm to 345 nm, e.g., a D98 of 342 nm.
  • Aspect 13 provides the aqueous dispersion according to any one of the preceding aspects, wherein the particles have a D90 in a range of 500 nm to 600 nm.
  • Aspect 14 provides the aqueous dispersion according to any one of the preceding aspects, wherein the aqueous dispersion is substantially free of phase separation between the plurality of particles and the surfactant component for a time period of greater than 1 month, preferably greater than 12 months.
  • Aspect 15 provides the aqueous dispersion according to any one of the preceding aspects, wherein the particles have a monomodal particle size distribution.
  • Aspect 16 provides the aqueous dispersion of any one of the preceding aspects, wherein the particles have a substantially spherical shape.
  • Aspect 17 provides the aqueous dispersion of any one of the preceding aspects, wherein the particles are substantially free of edges.
  • Aspect 18 provides the aqueous dispersion according to any one of Aspects 1-14, wherein the particles have a bimodal particle size distribution.
  • Aspect 19 provides the aqueous dispersion according to any one of the preceding aspects, wherein the particles have a sub-micron diameter.
  • Aspect 20 provides the aqueous dispersion according to any one of the preceding aspects, wherein the plasticizer component ranges from 1 wt% to 20 wt% of the aqueous dispersion, preferably wherein the aqueous dispersion comprises from 1 wt% to 30 wt% surfactant component, and wherein the total weight percentage in the aqueous dispersion is 100 wt%.
  • Aspect 21 provides the aqueous dispersion according to any one of the preceding aspects, wherein the plasticizer component ranges from 13 wt% to 16 wt% of the aqueous dispersion.
  • Aspect 22 provides the aqueous dispersion according to any one of the preceding aspects, wherein the plasticizer component comprises two or more plasticizers.
  • Aspect 23 provides the aqueous dispersion of Aspect 22, wherein one of the plasticizers ranges from 50 wt% to 100 wt% of the plasticizer component.
  • Aspect 24 provides the aqueous dispersion of Aspect 22, wherein one of the plasticizers ranges from 90 wt% to 100 wt% of the plasticizer component.
  • Aspect 25 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises a material chosen from an aliphatic monoalkyl ester, an aromatic monoalkyl ester, an aliphatic polyalkyl ester, an aromatic polyalkyl ester, a polyalkyl ester of an aliphatic alcohol, a phosphonic polyalkyl ester, an aliphatic poly(alkoxylated) ester, an aromatic poly(alkoxylated) ester, a poly(alkoxylated) ether of an aliphatic alcohol, a poly(alkoxylated) ether of a phenol, or mixtures thereof.
  • the plasticizer comprises a material chosen from an aliphatic monoalkyl ester, an aromatic monoalkyl ester, an aliphatic polyalkyl ester, an aromatic polyalkyl ester, a polyalkyl ester of an aliphatic alcohol, a phosphonic polyalkyl ester
  • Aspect 26 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises a material chosen from an organophosphorous compound, a halogenated compound, a metal hydroxide, or mixtures thereof.
  • Aspect 27 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises an organophosphorous compound which is chosen from triethyl phosphate, tris(2-chloropropyl)phosphate, triphenyl phosphate, diphenyl cresyl phosphate, resorcinol diphenylphosphate, resorcinol diphosphate, trialkyl phosphites, triaryl phosphites, mixed alkyl-aryl phosphites, diethyl ethyl phosphonate, dimethyl methyl phosphonate, melamine polyphosphate, ammonium polyphosphates, aluminum tris(diethyl phosphinate), or mixtures thereof.
  • organophosphorous compound which is chosen from triethyl phosphate, tris(2-chloropropyl)phosphate, triphenyl phosphate, diphenyl cresyl phosphate, resorcinol dipheny
  • Aspect 28 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises resorcinol diphenyl phosphate, preferably the plasticizer consists of resorcinol diphenyl phosphate.
  • Aspect 29 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises a halogenated compound which is chosen from a chlorendic acid derivative, a chlorinated paraffin; an organobromine, a decabromodiphenyl ether, a decabromodiphenyl ethane, a polymeric brominated compound, a brominated polystyrene, a brominated carbonate oligomer, a brominated epoxy oligomer, a tetrabromophthalic anyhydride, or mixtures thereof.
  • the plasticizer comprises a halogenated compound which is chosen from a chlorendic acid derivative, a chlorinated paraffin; an organobromine, a decabromodiphenyl ether, a decabromodiphenyl ethane, a polymeric brominated compound, a brominated polystyrene, a brominated carbonate oligomer, a
  • Aspect 30 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer comprises a metal hydroxide which is chosen from magnesium hydroxide, aluminum hydroxide, cobalt hydroxide, hydrates thereof, or mixtures thereof.
  • the plasticizer comprises a metal hydroxide which is chosen from magnesium hydroxide, aluminum hydroxide, cobalt hydroxide, hydrates thereof, or mixtures thereof.
  • Aspect 31 provides the aqueous dispersion according to any one of the preceding aspects, wherein a minimum film formation temperature of the aqueous dispersion ranges from 100 °C to 180 °C
  • Aspect 32 provides the aqueous dispersion according to any one of the preceding aspects, wherein a minimum film formation temperature of the aqueous dispersion ranges from 165 °C to 180 °C.
  • Aspect 33 provides the aqueous dispersion according to any one of the preceding aspects, wherein a minimum film formation temperature of the aqueous dispersion ranges from 10 °C to 50 °C less than a corresponding aqueous dispersion that is free of the plasticizer component.
  • Aspect 34 provides the aqueous dispersion of any one of the preceding aspects, wherein the plasticizer is resorcinol diphenyl phosphate.
  • Aspect 35 provides the aqueous dispersion according to any one of the preceding aspects, wherein the surfactant component ranges from 1 wt% to 20 wt% of the aqueous dispersion.
  • Aspect 36 provides the aqueous dispersion according to any one of the preceding aspects, wherein the surfactant component ranges from 5 wt% to 15 wt% of the aqueous dispersion.
  • Aspect 37 provides the aqueous dispersion according to any one of the preceding aspects, wherein the surfactant component comprises two or more surfactants.
  • Aspect 38 provides the aqueous dispersion of Aspect 37, wherein, when two or more surfactants are present, one of the surfactants comprises 50 wt% to 100 wt% of the surfactant component.
  • Aspect 39 provides the aqueous dispersion of Aspect 38, wherein one of the surfactants comprises 90 wt% to 100 wt% of the surfactant component.
  • Aspect 40 provides the aqueous dispersion of any one of the preceding aspects, wherein the surfactant comprises at least one of an anionic surfactant, a cationic surfactant, or a non-ionic surfactant.
  • Aspect 41 provides the aqueous dispersion of Aspect 40, wherein the surfactant comprises an anionic surfactant which is at least one of stearate sodium, dodecyl sulfate sodium, dodecyl benzene sulfonate sodium, alginic acid sodium, glycolic acid ethoxylate 4-tert butylphenyl ether, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate 4-nonylphenyl ether, poly(ethylene glycol) 4-nonylphenyl 3-sulfopropyl ether potassium salt, sodium dioctyl sulphosuccinate, or a mixture thereof.
  • the surfactant comprises an anionic surfactant which is at least one of stearate sodium, dodecyl sulfate sodium, dodecyl benzene sulfonate sodium, alginic acid sodium, glycolic acid ethoxylate 4-tert butyl
  • Aspect 42 provides the aqueous dispersion of any one of the preceding aspects, wherein the surfactant comprises a non-ionic surfactant which is at least one of poly(ethylene glycol) -Woc&-poly(propylene glycol)-Woc&-poly(ethylene glycol), poly(ethylene glycol) sorbitan tetraoleate, polyethylene-Woc&-poly(ethylene glycol), sorbitan monopalmitate, polyoxyethylenesorbtan monooleate, or a mixture thereof.
  • the surfactant comprises a non-ionic surfactant which is at least one of poly(ethylene glycol) -Woc&-poly(propylene glycol)-Woc&-poly(ethylene glycol), poly(ethylene glycol) sorbitan tetraoleate, polyethylene-Woc&-poly(ethylene glycol), sorbitan monopalmitate, polyoxyethylenesorbtan monooleate, or a mixture thereof.
  • Aspect 43 provides the aqueous dispersion according to any one of the preceding aspects, further comprising a solvent component.
  • Aspect 44 provides the aqueous dispersion of Aspect 43, wherein a solvent of the solvent component is selected from dichloromethane, chloroform, demethylformamide, dimethyl sulfate, tetrahydrofuran, or mixtures thereof.
  • Aspect 45 provides the aqueous dispersion of any one of the preceding aspects, further comprising an additive comprising a particulate filler, antioxidant, heat stabilizer, light stabilizer, ultraviolet light stabilizer, UV absorbing additive, NIR absorbing additive, IR absorbing additive, plasticizer, lubricant, release agent, antistatic agent, anti-fog agent, antimicrobial agent, colorant, laser marking additive, surface effect additive, radiation stabilizer, flame retardant, anti- drip agent, a fragrance, a fiber, or a mixture thereof.
  • an additive comprising a particulate filler, antioxidant, heat stabilizer, light stabilizer, ultraviolet light stabilizer, UV absorbing additive, NIR absorbing additive, IR absorbing additive, plasticizer, lubricant, release agent, antistatic agent, anti-fog agent, antimicrobial agent, colorant, laser marking additive, surface effect additive, radiation stabilizer, flame retardant, anti- drip agent, a fragrance, a fiber, or a mixture thereof.
  • Aspect 46 provides the aqueous dispersion of any one of the preceding aspects, further comprising a flow promoter comprising an unmodified fumed metal oxide, a hydrophobic fumed metal oxide, a hydrophilic fumed metal oxide, hydrated silica, amorphous alumina, glassy silica, glassy phosphate, glassy borate, glassy oxide, titania, talc, mica, kaolin, attapulgite, calcium silicate, magnesium silicate, or a mixture thereof.
  • a flow promoter comprising an unmodified fumed metal oxide, a hydrophobic fumed metal oxide, a hydrophilic fumed metal oxide, hydrated silica, amorphous alumina, glassy silica, glassy phosphate, glassy borate, glassy oxide, titania, talc, mica, kaolin, attapulgite, calcium silicate, magnesium silicate, or a mixture thereof.
  • Aspect 47 provides an article produced from the aqueous dispersion of any one of the preceding aspects, comprising: a plurality of particles, each particle comprising a polycarbonate component, wherein individual particles have a D90 in a range of 300 nm to 4000 nm; a plasticizer component; and a surfactant component.
  • Aspect 48 provides the article of Aspect 47, wherein the article is a sizing, is a film, a powder, a coating, a tie layer, an adhesive, a composite unidirectional tape, a three-dimensional printed article, or a woven.
  • Aspect 49 provides the article according to any one of Aspects 47-48, wherein the article is a tie layer to bond metal to a fluoropolymer, a powder coating, an epoxy-toughening coating, or a coating on a fiber.
  • Aspect 50 provides a method of forming the aqueous dispersion of any of Aspects 1 - 46, the method comprising: combining an organic phase and an aqueous phase to form an first solution, the organic phase comprising a polycarbonate component and a solvent component, the aqueous phase comprising water and a surfactant component; heating the first solution to evaporate the solvent and form a second solution; mixing at least one of the first solution and the second solution; and combining a plasticizer component with the second solution to form the aqueous dispersion.
  • Aspect 51 provides the method of Aspect 50, wherein combining the organic phase and the aqueous phase is performed in a drop-wise manner.
  • Aspect 52 provides the method of any of Aspects 50 - 51, wherein the mixing is under shear at 7,000 to 30,000 rpm
  • Aspect 53 provides the method of any of Aspects 50 - 52, wherein the mixing is under shear at 15,000 to 25,000 rpm
  • Aspect 54 provides the method of any of Aspects 50 -53, wherein the mixing is under high shear for 2 to 40 minutes.
  • Aspect 55 provides the method of any of Aspects 50 - 54, wherein the mixing is under high shear for 8 to 30 minutes.
  • Aspect 56 provides the method of any of Aspects 50 -55, further comprising removing the solvent component.
  • Aspect 57 provides the method of any of Aspects 50 - 56, wherein removing the solvent component comprises heating the second solution to a temperature at or above the boiling point of the solvent component but below the boiling point of the water.
  • Aspect 58 provides the method of any of Aspects 50 - 57, further comprising adding the second solution to a second aqueous composition.
  • Aspect 59 provides the method according to any one of Aspects 50-58, wherein the surfactant component is an anionic surfactant and the particles have a D90 in a range of 300 nm to 400 nm.
  • Aspect 60 provides the method according to any one of Aspects 50-59, wherein the surfactant component is an anionic surfactant and the particles have a D98 of 342 nm.
  • Aspect 61 provides a product formed according to the method of any one of Aspects 50-60.
  • Aspect 62 provides a sized carbon fiber tow, comprising: a polycarbonate sizing on a carbon fiber tow, wherein the polycarbonate sizing has a concentration of volatile organic compounds less than 10 ppm; and an average sizing content of at least 0.5 wt% of the carbon fiber tow with a coefficient of variation less than 15 %.
  • Aspect 63 provides the sized carbon fiber tow of Aspect 62, wherein the coefficient of variation in sizing content is less than 11 .
  • Aspect 64 provides the sized carbon fiber tow of any one of Aspects 62 - 63, wherein the concentration of volatile organic compounds is less than 5 ppm.
  • Aspect 65 provides the sized carbon fiber tow of any one of Aspects 62 - 64, wherein the concentration of volatile organic compounds is less than 2 ppm.
  • Aspect 66 provides the sized carbon fiber tow of any one of Aspects 62-65, wherein the average sizing content ranges from 0.9 wt% to 2.4 wt% of the carbon fiber tow.
  • Aspect 67 provides the sized carbon fiber tow of any one of Aspects 62-66, wherein the volatile organic compounds are members selected from the group consisting of methylene chloride, perchloro-ethylene, methyl-tertiary butyl ether (MTBE), N-Methyl-2-pyrrolidone, t- butyl acetate, dimethylformamide (DMF), dioxane, dichloromethane (DCM), n-alkane (C12- C18), dimethyl carbonate, cyclopentanone, chloroform, formaldehydes, acetone, toluene, xylene, benzene, hexane, diphenyl carbonate, and combinations thereof.
  • the volatile organic compounds are members selected from the group consisting of methylene chloride, perchloro-ethylene, methyl-tertiary butyl ether (MTBE), N-Methyl-2-pyrrolidone, t- butyl acetate
  • Aspect 68 provides a method of preparing the sized carbon fiber tow of any one of Aspects 62 - 67, comprising: spreading the carbon fiber tow over a spreader unit at a throughput line speed of at least 0.3 meters/minute and forming spreaded carbon fibers; sizing the spreaded carbon fibers in a sizing bath containing an aqueous polycarbonate sizing dispersion and forming sized carbon fibers; and drying the sized carbon fibers and obtaining the sized carbon fiber tow.
  • Aspect 69 provides the method according to Aspect 68, wherein the carbon fiber tow is optionally unspooled over a bobbin prior to spreading.
  • Aspect 70 provides the method according to any one of Aspects 68-69, wherein the sized carbon fiber tow is optionally winded into a spool for further processing.
  • Aspect 71 provides the method of any one of Aspects 68- 70, wherein the sized carbon fibers are dried in an oven operating at a temperature ranging from 150° C to 300° C.
  • Aspect 72 provides the method of any one of Aspects 68-71, wherein the aqueous polycarbonate sizing dispersion comprises: a polycarbonate component comprising, a plurality of polycarbonate resin particles, wherein the plurality of polycarbonate resin particles has a dispersion characterized by having a D90 value ranging from 300 nm to 4000 nm; a plasticizer component; and a surfactant component.
  • Aspect 73 provides the method of any one of Aspects 68-71, wherein the aqueous polycarbonate sizing dispersion is the aqueous dispersion of any one of Aspects 1 - 46.
  • Aspect 74 provides the method according to any one of Aspects 72-73, wherein the plurality of polycarbonate resin particles is present at a concentration ranging from 0.5 wt% to 5 wt% of the aqueous polycarbonate sizing dispersion.
  • Aspect 75 provides the method according to any one of Aspect 72-74, wherein the aqueous polycarbonate sizing dispersion has a minimum film formation temperature (MFFT) ranging from 100 °C to 180 °C.
  • Aspect 76 provides the method according to any one of Aspects 72-75, wherein the plurality of polycarbonate resin particles has a monomodal size distribution.
  • Aspect 77 provides the method according to any one of Aspects 72-76, wherein the plasticizer component comprises a member selected from the group consisting of esters, organophosphorous compounds, ethers, hydrocarbons, paraffins, sulphonamides, sulfonates, terephthalates, terpenes, trimellitates, and combinations thereof.
  • Aspect 78 provides the method according to any one of Aspects 72-77, wherein the plasticizer component comprises an organo-phosphorous compound selected from a group consisting of resorcinol bis-(diphenylphosphate) (RDP), trialkyl phosphates, triaryl phosphates, phosphites, phosphonates, polyphosphates, polyphosphites, polyphosphonates, phosphinates, and combinations thereof .
  • RDP resorcinol bis-(diphenylphosphate)
  • Aspect 79 provides the method according to any one of Aspects 72-78, wherein the plasticizer component is resorcinol bis-(diphenylphosphate) (RDP).
  • RDP resorcinol bis-(diphenylphosphate)
  • Aspect 80 provides the method according to any one of Aspects 72-79, wherein the plasticizer component is present at a concentration ranging from 1 wt% to 20 wt% of the aqueous polycarbonate sizing dispersion.
  • Aspect 81 provides the method according to any one of Aspects 72-80, wherein the surfactant component is selected from a group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, and blends thereof.
  • Aspect 82 provides the method according to any one of Aspects 72-81, wherein the surfactant component is present at a concentration ranging from 1 wt% to 20 wt% of the aqueous polycarbonate sizing dispersion.

Abstract

La présente invention concerne, selon divers modes de réalisation, une dispersion aqueuse. La dispersion aqueuse comprend une pluralité de particules. Chacune des particules comprend un constituant polycarbonate. Les particules individuelles du constituant polycarbonate ont sensiblement la même taille. La dispersion comprend en outre un constituant plastifiant et un constituant tensioactif. Dans un mode de réalisation, une mèche de fibres de carbone ensimée peut comprendre : un ensimage à base de polycarbonate sur une mèche de fibres de carbone, l'ensimage à base de polycarbonate ayant une concentration en composés organiques volatils inférieure à 10 ppm, de préférence inférieure à 5 ppm, ou inférieure à 2 ppm ; et une teneur moyenne en ensimage d'au moins 0,5 % en poids de la mèche de fibres de carbone, un coefficient de variation étant inférieur à 15 %, de préférence inférieur à 11 %.
EP18772864.7A 2017-08-01 2018-08-01 Dispersions polymères aqueuses, procédés de fabrication de telles dispersions polymères aqueuses et mèches de fibres ensimées Withdrawn EP3638842A1 (fr)

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EP2013408B2 (fr) * 2006-05-02 2016-09-28 Rohr, Inc. Nacelles et ses composants utilisant des nanorenforcements
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