Polymer compositions and articles made therefrom - Patents.com

Abstract

A polymer composition and articles made therefrom are provided. The polymer composition comprises 25-50 wt. % thermoplastic polymer, 10-45 wt. % thermally conductive filler, 15-30 wt. % electrically conductive carbon fiber, and less than 5 wt. % additives. The polymer composition is substantially free of glass fiber. The polymer composition described herein surprisingly exhibits significantly improved thermal conductivity compared to a similar polymer composition in which the carbon fiber is replaced with glass fiber. Furthermore, despite the fact that carbon fiber has a significantly higher electrical conductivity compared to glass fiber, the polymer composition does not have a noticeable loss in volume resistivity compared to a similar polymer composition in which the carbon fiber is replaced with glass fiber.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 225,627, filed July 26, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] A thermally conductive and electrically resistive polymeric composition is provided. Articles made therefrom are also provided. In particular, the polymeric composition of the present invention includes a thermoplastic polymer and a combination of a thermally conductive filler and an electrically conductive carbon fiber. [Background technology]

[0003] Polymer compositions are used in many applications including motors, batteries, LEDs, electronic circuit boards, etc. In many of these, it may be desirable for the polymer composition to function to help dissipate heat from heat-generating components. While thermal conductivity may be desired, electrical conductivity is often contraindicated, and polymer compositions used in such applications are expected to have a volume resistivity of at least 1E+8 Ω·cm.

[0004] Polymer compositions intended for use in these environments have typically used fillers that are purely thermally conductive. However, polymer compositions containing only thermally conductive fillers have limited in-plane and cross-plane thermal conductivity. This is believed to be due to the inherent thermal conductivity limitations of the fillers and / or thermal resistance at the polymer / filler interface. As a result, the use of high concentrations of purely thermally conductive fillers in polymer compositions to achieve the desired electrical conductivity may not have the expected or desired effect.

[0005] There is a need for polymer compositions that exhibit both thermal conductivity and electrical resistivity, desirably without compromising the mechanical performance of the polymer composition. Summary of the Invention

[0006] 1. A polymer composition comprising: - 25-50% by weight of a thermoplastic polymer; - 10-45% by weight of a thermally conductive filler; - 15-30% by weight of conductive carbon fibers; - less than 5% by weight of additives; wherein the weight percent is based on the total weight of the polymer composition; The polymer composition is substantially free of glass fibers; A polymer composition is provided, in some embodiments, in which the ratio of the total weight of the conductive carbon fibers to the total weight of all non-thermoplastic polymer components in the polymer composition is less than 1:3.8.

[0007] Also provided are articles comprising the polymeric compositions, e.g., selected from the group consisting of structural or functional parts of i) electronic devices, ii) automobiles, iii) motors, iv) batteries, v) LEDs, vi) electronic boards, vii) electric vehicle charging stations, viii) vacuums or vacuum systems, and the like. [Brief description of the drawings]

[0008] [Figure 1] 1 is a bar graph showing the in-plane thermal conductivity of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Diagram 2] 1 is a bar graph showing the effect of adding conductive carbon fibers to comparative (C5 and C6) and inventive (E1-E4) polymer compositions. [Diagram 3] 1 is a bar graph showing the tensile modulus of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Figure 4] 1 is a bar graph showing the flexural modulus of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Provided is a polymer composition comprising a thermoplastic polymer, at least one thermally conductive filler, and conductive carbon fibers. Importantly, the polymer composition is substantially free of glass fibers. Surprisingly, it has been found that the polymer composition described herein has significantly improved thermal conductivity compared to a similar polymer composition in which carbon fibers are replaced with glass fibers. It has also been found surprisingly that the polymer composition does not have a noticeable loss in volume resistivity compared to a similar polymer composition in which carbon fibers are replaced with glass fibers, despite the fact that carbon fibers have significantly higher electrical conductivity compared to glass fibers. Furthermore, the tensile and flexural moduli of the polymer composition containing carbon fibers are surprisingly increased compared to a similar polymer composition in which carbon fibers are replaced with glass fibers.

[0010] As used herein, a polymeric composition that is "substantially free" of a indicated component (e.g., glass fiber) has a concentration of the indicated component of less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, where weight percent is based on the total weight of the polymeric composition unless otherwise specified.

[0011] Any description, even if described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Further, any element or component recited in a list of elements or components may be omitted from such list.

[0012] Any recitation of numerical ranges by endpoints includes all numbers and subranges subsumed within the recited range, as well as the endpoints of the range.

[0013] As used herein, the mol % of a particular repeat unit is determined relative to the total number of repeat units in the indicated polymer, unless expressly indicated otherwise.

[0014] The amount of energy in the form of heat required to cause a thermoplastic polymer to change state from a solid to a liquid form is called the heat of fusion (ΔHf "), and the temperature at which this state change occurs is called the melting temperature (Tm). ΔH f and Tm can be measured according to ASTM D3418.

[0015] The glass transition temperature (Tg) is the temperature at which an amorphous material (or amorphous regions within a semicrystalline material) transitions from a hard, relatively brittle state to a viscous or rubber-like state. Tg can be measured according to ASTM E1356 "Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry."

[0016] The term "halogen" or "halo" includes fluorine, chlorine, bromine, and iodine.

[0017] Unless specifically limited otherwise, the terms "alkyl" and derived terms such as "alkoxy", "acyl" and "alkylthio", as used herein, include within their scope straight chain, branched chain and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl.

[0018] Similarly, unless specifically limited otherwise, the term "aryl" refers to a phenyl, indanyl, or naphthyl group. An aryl group may contain one or more alkyl groups, in which case it may be referred to as an "alkylaryl." For example, an aromatic group may be substituted with one or more C1-C6 alkyl groups, such as methyl or ethyl.

[0019] An aryl group may also contain one or more heteroatoms, such as N, O, or S, and in such cases may be appropriately referred to as a "heteroaryl" group. Such heteroaromatic rings may be fused to other aromatic systems. Examples of heteroaromatic rings include, but are not limited to, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl, and triazinyl ring structures.

[0020] Unless otherwise specifically stated, each alkyl, aryl, and heteroaryl group may be unsubstituted or substituted with one or more substituents selected from, but not limited to, halogen, hydroxy, sulfo, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C15 aryloxy, or C6-C15 aryl, provided that the substituents are also sterically compatible and chemical bonding and strain energy rules are satisfied.

[0021] Thermoplastic Polymers The polymer composition comprises a thermoplastic polymer. Generally, any thermoplastic polymer can benefit from the application of the principles described herein, but those contemplated for use in applications where high thermal conductivity and electrical resistance are desired are of particular interest. Thermoplastic polymers suitable for use in the polymer composition include, but are not limited to, poly(arylene sulfide), polyamide, poly(aryl ether sulfone), poly(aryl ether ketone), liquid crystal polymer, and / or polyester.

[0022] In some embodiments, the polymer composition comprises at least 15%, at least 20%, or at least 25% by weight of thermoplastic polymer. In some embodiments, the polymer composition comprises no more than 60%, no more than 55%, or no more than 50% by weight of thermoplastic polymer. In some embodiments, the polymer composition comprises between 15% and 60%, between 20% and 55%, or between 25% and 50% by weight of thermoplastic polymer.

[0023] In some embodiments, the polymer composition can include multiple thermoplastic polymers, including but not limited to those listed above, in such embodiments, the total concentration of thermoplastic polymers is within the ranges stated above.

[0024] In some embodiments, the thermoplastic polymer is semi-crystalline. As used herein, a semi-crystalline polymer has a heat of fusion ("ΔH") of at least 5 J / g. f "). Thus, in some embodiments, the thermoplastic polymer has a ΔH of at least 5 J / g, at least 10 J / g, at least 20 J / g, or at least 25 J / g. f (heating rate of 20° C. / min). In some embodiments, the thermoplastic polymer has a ΔH of 90 J / g or less, 80 J / g or less, 70 J / g or less, or 60 J / g or less. f In some embodiments, the thermoplastic polymer has a ΔH of 5 J / g to 90 J / g, 10 J / g to 80 J / g, 20 J / g to 70 J / g, or 25 J / g to 60 J / g. f has.

[0025] Poly(arylene sulfide) In some embodiments, the thermoplastic polymer is a poly(arylene sulfide) (PAS). As used herein, poly(arylene sulfide) is a polymer having a repeating unit (R PAS ) refers to any polymer that contains at least 50 mol % of: -[-Ar-S-]- (I) where Ar is arylene.

[0026] In some embodiments, the repeating unit (R PAS ) is represented by a formula selected from the group of formulas: [ka] (In the formula, R, in each case, is halogen, C1-C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene group, C1-C 12 Alkoxy groups and C6-C 18 aryloxy groups; - T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2-, -C(CF3)2-, phenyl, and -CH2-; - i, at each occurrence, is independently an integer from 0 to 4; - j, in each occurrence, is independently an integer from 0 to 3.

[0027] Repeating unit (R PAS In the formula (I), each phenylene moiety may independently have a 1,2-, 1,3-, or 1,4-bond to a moiety other than R. In some embodiments, each phenylene moiety independently has a 1,3- or 1,4-bond to a moiety other than R. Preferably, the phenylene moieties have a 1,4-bond to a moiety other than R.

[0028] In one embodiment, -Ar- in formula (I) is a phenyl group, and therefore the repeat unit (R PAS Preferably, -Ar- in formula (I) is represented by formula (II) in which i is 0 and the phenylene moiety has a 1,4-bond to a moiety other than R, and thus the repeat unit (R PAS ) is represented by the following formula (II'): [ka]

[0029] In such embodiments, the poly(arylene sulfide) is polyphenylene sulfide.

[0030] In some embodiments, the repeat units (R PAS ) is at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol%. In such embodiments, the poly(arylene sulfide) comprises repeat units (R PAS In another embodiment, the poly(arylene sulfide) consists essentially of repeat units (R PAS ) is 100 mol %, and in these embodiments, the poly(arylene sulfide) has a repeat unit (R PAS )

[0031] In some embodiments, the poly(arylene sulfide) has a weight average molecular weight ("M") of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, or at least 35,000 g / mol. w In some embodiments, the poly(arylene sulfide) has an M of 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 85,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the poly(arylene sulfide) has an M of 10,000 g / mol to 150,000 g / mol, 20,000 g / mol to 100,000 g / mol, 25,000 g / mol to 90,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 35,000 g / mol to 80,000 g / mol. w The M of poly(arylene sulfide)w can be measured using gel permeation chromatography ("GPC") using a 4-chloronaphthalene standard.

[0032] In some embodiments, the poly(arylene sulfide) has a Tm of at least 200° C., at least 220° C., at least 240° C., or at least 250° C. In some embodiments, the poly(arylene sulfide) (PAS) has a Tm of 350° C. or less, 320° C. or less, 300° C. or less, or 285° C. or less. In some embodiments, the poly(arylene sulfide) (PAS) has a Tm of 200° C. to 350° C., 220° C. to 320° C., 240° C. to 300° C., or 250° C. to 285° C.

[0033] The poly(phenylene sulfide) (poly(arylene sulfide) according to formula (II')) may have a melt flow rate (316°C, 5 kg load, according to ASTM D1238, procedure B) of 50 to 400 g / 10 min, 60 to 300 g / 10 min, or 70 to 200 g / 10 min.

[0034] The poly(arylene sulfides) and poly(phenylene sulfides) can be prepared by known methods.

[0035] polyamide In some embodiments, the thermoplastic polymer is a polyamide (PA). Polyamide refers to a polymer that contains at least 50 mol % of repeat units having at least one amide bond (-CONH-). In some embodiments, a polyamide is a polymer that contains repeat units (R PA ) including: [ka] (In the formula, - R2 is a bond, C1~C 15 Alkyl and C6-C 30 aryl; - R3 is C1~C 20Selected from the group consisting of alkyl, phenyl, indanyl, and naphthyl; - R2 and R3 each independently optionally contain one or more heteroatoms (e.g., O, N, or S) and optionally include halogen, hydroxy (-OH), sulfo (-SO3H), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy and C6-C 15 aryl).

[0036] In some embodiments, R3 of formula (V) is phenyl and the polyamide is a polyphthalamide according to formula (VI): [ka]

[0037] In some embodiments, the polyamide comprises at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of repeat units R according to formula (V) and / or (VI). PA In such an embodiment, the polyamide comprises repeat units (R PA In another embodiment, the polyamide consists essentially of repeat units (R ) according to formula (V) and / or (VI). PA According to such an embodiment, the polyamide comprises repeating units (R PA )

[0038] In some embodiments, the polyamide has an M of at least 15,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, or at least 35,000 g / mol. wIn some embodiments, the polyamide has an M of 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 85,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the polyamide has an M of 15,000 g / mol to 150,000 g / mol, 20,000 g / mol to 100,000 g / mol, 25,000 g / mol to 90,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 35,000 g / mol to 80,000 g / mol. w Polyamide M w can be measured using gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0039] In some embodiments, the polyamide has a Tm of at least 200° C., at least 220° C., at least 240° C., or at least 250° C. In some embodiments, the polyamide has a Tm of 370° C. or less, 360° C. or less, 350° C. or less, or 340° C. In some embodiments, the polyamide has a Tm of 200° C. to 370° C., 220° C. to 360° C., 240° C. to 350° C., or 250° C. to 340° C.

[0040] The polyamides and polyphthalamides can be prepared by known methods.

[0041] Poly(aryl ether sulfone) According to one embodiment, the thermoplastic polymer is a poly(arylethersulfone) (PAES), which includes, but is not limited to, polysulfone, polyphenylsulfone, and polyethersulfone.

[0042] Poly(aryl ether sulfone) is a compound represented by the formula (VII): [ka] Repeating units (R PAESIn formula (VII), - R, at each occurrence, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkylsulfonate, alkali metal or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium; - i for each R is independently an integer from 0 to 4; - T is a bond, a sulfone group [-S(=O) 2- ], and groups of formula (VIII) -C(R2)(R2)- (VIII) and in formula (VIII), R2, at each occurrence, is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkylsulfonate, alkali metal or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium.

[0043] T is preferably a bond (i.e. the polyarylethersulfone is a polyphenylsulfone), a sulfone group (i.e. the polyarylethersulfone is a polyethersulfone), or a group according to formula (VIII) in which each R2 is a methyl group (i.e. the polyarylethersulfone is a polysulfone).

[0044] Repeating unit (R PAES In the formula (I), each phenylene moiety may independently have 1,2-, 1,3-, or 1,4-bonds to moieties other than R. In some embodiments, each phenylene moiety independently has 1,3- or 1,4-bonds to moieties other than R. Preferably, the phenylene moieties have 1,4-bonds to moieties other than R.

[0045] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of the repeat units in the poly(aryl ether sulfone) are repeat units (R PAES In such embodiments, the poly(aryl ether sulfone) comprises the repeating unit (R PAES In another embodiment, the poly(aryl ether sulfone) has 100 mol % of the repeat units consisting essentially of the repeat unit (R PAES According to such an embodiment, the poly(aryl ether sulfone) has the repeating unit (R PAES )

[0046] The poly(aryl ether sulfone) can have a Mw of 30,000 g / mol to 80,000 g / mol, for example, 35,000 g / mol to 75,000 g / mol, or 40,000 g / mol to 70,000 g / mol. The Mw of the poly(aryl ether sulfone) can be determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase (Agilent Technologies 2×5μ mixed D column with guard column; flow rate: 1.5 mL / min, injection volume: 20 μL of 0.2 w / v% sample solution) with polystyrene standards.

[0047] In some embodiments, the poly(aryl ether sulfone) has a Tg of at least 150° C., at least 160° C., at least 170° C., or at least 180° C. In some embodiments, the poly(aryl ether sulfone) has a Tg of 270° C. or less, 260° C. or less, 250° C. or less, or 240° C. In some embodiments, the poly(aryl ether sulfone) has a Tg of 150° C. to 270° C., 160° C. to 260° C., 170° C. to 250° C., or 170° C. to 240° C.

[0048] The poly(aryl ether sulfone)s can be prepared by known methods.

[0049] Polysulfone In some embodiments, the thermoplastic polymer is a poly(aryl ether sulfone), and the poly(aryl ether sulfone) is a polysulfone (PSU). As used herein, polysulfone refers to a polymer having a repeating unit (R PSU ) refers to any polymer that contains at least 50 mol % of: [ka] (In the formula, - R, at each occurrence, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkylsulfonate, alkali metal or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium; - each i in R is independently an integer from 0 to 4.

[0050] In one embodiment, for each R in formula (VII-A), i is 0. According to this embodiment, the repeat unit (R PSU ) is a unit of formula (VII-B): [ka]

[0051] Repeating unit (R PSU In the formula (I), each phenylene moiety may independently have 1,2-, 1,3-, or 1,4-bonds to moieties other than R. In some embodiments, each phenylene moiety independently has 1,3- or 1,4-bonds to moieties other than R. Preferably, the phenylene moieties have 1,4-bonds to moieties other than R.

[0052] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of the repeat units in the polysulfone are repeat units of formula (VII-A) and / or formula (VII-B) (R PSU In such an embodiment, the polysulfone comprises repeat units (R PSU In another embodiment, the polysulfone essentially consists of 100 mol % of the repeating units of formula (VII-A) and / or formula (VII-B) (R PSU According to such an embodiment, the polysulfone comprises repeat units (R PSU )

[0053] In some embodiments, the Mw of the polysulfone is 30,000-80,000 g / mol, e.g., 35,000-75,000 g / mol, or 40,000-70,000 g / mol. The Mw of the polysulfone can be determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase (Agilent Technologies 2×5μ mixed D column with guard column; flow rate: 1.5 mL / min, injection volume: 20 μL of 0.2 w / v% sample solution) with polystyrene standards.

[0054] In some embodiments, the polysulfone has a Tg of at least 150° C., at least 160° C., at least 170° C., or at least 180° C. In some embodiments, the polysulfone has a Tg of 270° C. or less, 260° C. or less, 250° C. or less, or 240° C. In some embodiments, the polysulfone has a Tg of 150° C.-270° C., 160° C.-260° C., 170° C.-250° C., or 170° C.-240° C.

[0055] The polysulfone can be produced by known methods.

[0056] Polyphenylsulfone In some embodiments, the thermoplastic polymer is a poly(aryl ether sulfone), and the poly(aryl ether sulfone) is a polyphenylsulfone (PPSU). As used herein, polyphenylsulfone refers to a polymer having a repeating unit (R PPSU ) refers to any polymer that contains at least 50 mol % of: [ka]

[0057] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of all repeat units in the polyphenylsulfone are repeat units (R PPSU In such an embodiment, the polyphenylsulfone is a repeating unit (R PPSU In another embodiment, the polyphenylsulfone is a polyphenylsulfone in which 100 mol % of the repeat units consist essentially of the repeat unit (R PPSU According to such an embodiment, the polyphenylsulfone is a repeating unit (R PPSU )

[0058] In some embodiments, the polyphenylsulfone has an M of at least 20,000 g / mol, at least 30,000 g / mol, or at least 40,000 g / mol. w In some embodiments, the polyphenylsulfone has an M of 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the polyphenylsulfone has an M of 20,000 g / mol to 100,000 g / mol, or 30,000 g / mol to 90,000 g / mol, or 40,000 g / mol to 80,000 g / mol. w The polyphenylsulfone Mw can be measured using gel permeation chromatography ("GPC") using polystyrene standards.

[0059] In some embodiments, the polyphenylsulfone has a Tg of at least 150° C., at least 160° C., at least 170° C., or at least 180° C. In some embodiments, the polyphenylsulfone has a Tg of 270° C. or less, 260° C. or less, 250° C. or less, or 240° C. In some embodiments, the polyphenylsulfone has a Tg of 150° C. to 270° C., 160° C. to 260° C., 170° C. to 250° C., or 170° C. to 240° C.

[0060] Polyphenylsulfone can be produced by a known method.

[0061] Polyethersulfone In some embodiments, the thermoplastic polymer is a poly(aryl ether sulfone), and the poly(aryl ether sulfone) is a polyether sulfone (PES). As used herein, polyether sulfone refers to a polymer having a repeating unit (R PES ) refers to any polymer that contains at least 50 mol % of: [ka]

[0062] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or 99.9 mol% of the repeat units in the polyethersulfone are repeat units (R PES In such an embodiment, the polyethersulfone is a repeating unit (R PES ) essentially consists of

[0063] In another embodiment, the polyethersulfone is a polyethersulfone in which 100 mol % of the repeating units are the repeating units (RPES According to such an embodiment, the polyethersulfone is a repeating unit (R PES )

[0064] In some embodiments, the polyethersulfone has an M of at least 20,000 g / mol, at least 30,000 g / mol, or at least 40,000 g / mol. w In some embodiments, the polyethersulfone has an M of 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the polyethersulfone has an M of 20,000 g / mol to 100,000 g / mol, 30,000 g / mol to 90,000 g / mol, or 40,000 g / mol to 80,000 g / mol. w The polyethersulfone M w can be measured using gel permeation chromatography ("GPC") using polystyrene standards.

[0065] In some embodiments, the polyethersulfone has a Tg of at least 150° C., at least 160° C., at least 170° C., or at least 180° C. In some embodiments, the polyethersulfone has a Tg of 270° C. or less, 260° C. or less, 250° C. or less, or 240° C. In some embodiments, the polyethersulfone has a Tg of 150° C. to 270° C., 160° C. to 260° C., 170° C. to 250° C., or 170° C. to 240° C.

[0066] Polyethersulfone can be produced by known methods.

[0067] Poly(aryl ether ketone) (PAEK) In some embodiments, the thermoplastic polymer is a poly(aryl ether ketone) (PAEK).

[0068] Poly(aryl ether ketone) refers to a repeating unit (R ) that contains an Ar′C(═O)Ar* group, where Ar′ and Ar* are the same or different and are aromatic groups. PAEK ) refers to any polymer that contains at least 50 mol %

[0069] In this specification, the repeating unit (R PAEK ) are repeat units of formulae (VIII) to (XI): [ka] (In the formula, - each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium, each substitutable group being understood to be substituted or unsubstituted, and, if substituted, to contain one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, and amine and quaternary ammonium groups; - i is independently an integer from 0 to 4.

[0070] Repeating unit (R PAEK ), each phenylene moiety is independently a repeat unit (R PAEK ) may have 1,2-, 1,4-, or 1,3-bonds to other moieties than R. In some embodiments, the phenylene moieties each independently have 1,3- or 1,4-bonds to moieties other than R. Preferably, the phenylene moieties have 1,4-bonds to moieties other than R.

[0071] Repeating unit (R PAEK In some embodiments of formulas (VIII)-(XI), for each R, i is 0. According to this embodiment, the repeat unit (R PAEK ) are represented by formulae (VIII-A) to (XI-A): [ka]

[0072] At least 50% of the repeat units are repeat units (R PAEK ), are also understood by those skilled in the art to be in the poly(ether ether ketone) (PEEK) genus.

[0073] According to one embodiment, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of the repeat units in the poly(aryl ether ketone) are repeat units (R PAEK In such embodiments, the poly(aryl ether ketone) comprises repeat units (R PAEK ) essentially consists of

[0074] In another embodiment, the poly(aryl ether ketone) has 100 mol % of repeat units of formula (VIII), formula (IX), formula (X), and / or formula (XI) (R PAEK According to such embodiments, the poly(aryl ether ketone) comprises repeat units (R PAEK )

[0075] In some embodiments, the poly(aryl ether ketone) has an M of at least 30,000 g / mol, at least 40,000 g / mol, or at least 50,000 g / mol. w In some embodiments, the poly(aryl ether ketone) has an M of 200,000 g / mol or less, 175,000 g / mol or less, or 150,000 g / mol or less. wIn some embodiments, the poly(aryl ether ketone) has an M of 30,000 g / mol to 200,000 g / mol, 40,000 g / mol to 175,000 g / mol, or 50,000 g / mol to 150,000 g / mol. w The poly(aryl ether ketone) M w can be measured using gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0076] In some embodiments, the poly(aryl ether ketone) has a Tm of at least 270° C., at least 280° C., at least 290° C., or at least 300° C. In some embodiments, the poly(aryl ether ketone) has a Tm of 400° C. or less, 390° C. or less, 380° C. or less, or 370° C. In some embodiments, the poly(aryl ether ketone) has a Tm of 270° C.-400° C., 280° C.-390° C., 290° C.-380° C., or 280° C.-370° C.

[0077] The poly(aryl ether ketones) and poly(ether ether ketones) can be prepared by known methods.

[0078] Liquid Crystal Polymer In some embodiments, the thermoplastic polymer is a liquid crystal polymer formed from the polycondensation of terephthalic acid, an aromatic diol, a first aromatic dicarboxylic acid different from terephthalic acid, and an aromatic hydroxycarboxylic acid.

[0079] In some embodiments, the aromatic diol is represented by a formula selected from formulas (XII) and (XIII): HO-Ar1-OH (XII) HO-Ar2-T1-Ar3-OH (XIII) (In the formula, - Ar1-Ar3 are halogens, C1-C 15 Alkyl and C6-C 15and independently selected C6-C aryl, optionally substituted with one or more substituents selected from the group consisting of 30 is an aryl group; - T1 is a bond, O, S, -SO2-, -C(=O)-, and C1 to C 15 and akyl.

[0080] In some embodiments, the aromatic diol is selected from the group consisting of 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,5-biphenyldiol, 4,4'-biphenol, 4,4'-(propane-2,2-diyl)diphenol, 4,4'-(ethane-1,2-diyl)diphenol, 4,4'-methylenediphenol, bis(4-hydroxyphenyl)methanone, 4,4'-oxydiphenol, 4,4'-sulfonyldiphenol, 4,4'-thiodiphenol, naphthalene-2,6-diol, and naphthalene-1,5-diol. Preferably, the aromatic diol is 4,4'-biphenol.

[0081] In some embodiments, the first aromatic dicarboxylic acid is represented by a formula independently selected from formulas (XIV) and (XV): HOOC-Ar1-COOH (XIV) HOOC-Ar2-T2-Ar3-COOH (XV) wherein Ar1-Ar3 are as defined above and are independently selected, and T2 is selected from the group consisting of a bond, O, and S.

[0082] In some embodiments, the first aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-oxydibenzoic acid, 4,4'-(ethylenedioxy)dibenzoic acid, 4,4'-sulfanediyldibenzoic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, and naphthalene-2,3-dicarboxylic acid. Preferably, the first aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, and naphthalene-2,3-dicarboxylic acid. Most preferably, the first aromatic dicarboxylic acid is isophthalic acid.

[0083] In some embodiments, the aromatic hydroxycarboxylic acid is represented by a formula selected from formulas (XVI) and (XVII): HO-Ar1-COOH (XVI) HO-Ar2-Ar3-COOH (XVII) (wherein Ar1-Ar3 are defined above and are independently selected).

[0084] In some embodiments, the aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 5-hydroxy-1-naphthoic acid, and 4'-hydroxy-[1,1'-biphenyl]-4-carboxylic acid. Preferably, the aromatic hydroxycarboxylic acid is selected from the group consisting of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 5-hydroxy-1-naphthoic acid. Most preferably, the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid.

[0085] In this specification, LCP refers to a polymer formed from the above-mentioned monomers and having repeating units (R LCP ) refers to any polymer having at least 50%: [ka] -[-O-Ar1-O-]- (XIX) -[-O-Ar2-T1-Ar3-O-]- (XX) -[-OC-Ar1-CO-]- (XXI) -[-OC-Ar2-T2-Ar3-CO-]- (XXII) -[-O-Ar1-CO-]- (XXIII) -[-O-Ar2-Ar3-CO-]- (XXIV) (wherein Ar1-Ar3, T1, and T2 are defined above and are independently selected).

[0086] Those skilled in the art will recognize that R LCP is formed from terephthalic acid; R according to the formulas (XIX) and (XX) LCP are formed from monomers according to formulae (XII) and (XIII), respectively; R according to formulae (XXI) and (XXII) LCP are formed from monomers according to formulae (XIV) and (XV), respectively; R according to formulae (XXIII) and (XXIV) LCP It will be appreciated that the repeat units R according to formulae (XIX) to (XIXV) are formed from monomers according to formulae (XVI) and (XVII). Therefore, the selection of Ar1 to Ar3, T1, and T2 for the monomers in formulae (XII) to (XVII) is dependent on the repeat units R according to formulae (XIX) to (XIXV). LCP Ar1 to Ar3, T1, and T2 are also selected for the repeat unit R according to formula (XVIII) LCP is formed by polycondensation of terephthalic acid, and has repeating units R according to the formulae (XIX) and (XX) LCP is formed by polycondensation of 4,4'-biphenol, and the repeating units R according to formulas (XXI) and (XXII) LCPis formed by polycondensation of isophthalic acid, and the repeating units R according to the formulae (XXIII) and (XXIV) LCP is formed by polycondensation of 4-hydroxybenzoic acid.

[0087] In some embodiments, the repeat unit R according to formula (XVIII)-(XXIV) LCP is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol%.

[0088] In some embodiments, the repeat unit R according to formula (XVIII) LCP In some embodiments, the concentration of repeat units R according to formula (XIX) and / or (XX) is 5 mol % to 30 mol %, preferably 10 mol % to 20 mol %. LCP In some embodiments, the concentration of repeat units R according to formulas (XXI) and (XXII) is 10 mol % to 30 mol %, preferably 15 mol % to 25 mol %. LCP In some embodiments, the concentration of repeat units R according to formulas (XXIII) and (XXIV) is 1 mol % to 20 mol %, preferably 1 mol % to 10 mol %. LCP The concentration of is 35 mol % to 80 mol %, preferably 45 mol % to 75 mol %, and most preferably 50 mol % to 70 mol %.

[0089] In some embodiments, the LCP has a Mw of at least 20,000 g / mol. In some embodiments, the LCP has a Mw of 80,000 g / mol or less. In some embodiments, the LCP has a Mw of 20,000 g / mol to 80,000 g / mol. Mw can be measured by gel permeation chromatography (GPC) according to ASTM D5296 and using hexafluoropropanol solvent and poly(methyl methacrylate) standards.

[0090] In some embodiments, the LCP has a Tm of at least 220° C., at least 250° C., or at least 280° C. In some embodiments, the LCP has a Tm of 420° C. or less, 390° C. or less, or 360° C. or less. In some embodiments, the LCP has a Tm of 220° C.-420° C., 250° C.-390° C., or 280° C.-360° C.

[0091] The liquid crystal polymer can be produced by a known method.

[0092] polyester In some embodiments, the thermoplastic polymer is a polyester. As used herein, a polyester is defined as a polymer having repeating units (R PE In some embodiments, a polyester refers to any polymer that comprises at least 50 mol % of repeating units (R PE ) including: [ka] (In the formula, - R1 and R2 are each independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - T is a bond or a substituted alicyclic group containing a monovalent alkyl group and a monovalent alicyclic group; - i is an integer from 0 to 4; - j is an integer from 0 to 2; - n is an integer from 1 to 12.

[0093] Repeating unit (R PEIn the formula (I), each phenylene moiety may independently have 1,2-, 1,3-, or 1,4-bonds to moieties other than R. In some embodiments, each phenylene moiety independently has 1,3- or 1,4-bonds to moieties other than R. Preferably, the phenylene moieties have 1,4-bonds to moieties other than R.

[0094] In some embodiments, i and j are each 0, T is a bond, and / or n is 1, 2, or 4. In some such embodiments, the polyester polymer is polytrimethylene terephthalate (i and j are 0, T is a bond, and n is 1); polyethylene terephthalate (i and j are 0, T is a bond, and n is 2); or polybutylene terephthalate (i and j are 0, T is a bond, and n is 4).

[0095] In some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, or at least 99.9 mol% of the repeat units in the polyester are repeat units (R PE In such an embodiment, the polyester has the repeating unit (R PE In another embodiment, the polyester is a polyester in which 100 mol % of the repeat units are essentially the repeat units (R PE According to such an embodiment, the polyester is a repeating unit (R PE )

[0096] In some embodiments, the polyester has an M of at least 10,000 g / mol, at least 20,000 g / mol, or at least 30,000 g / mol. w In some embodiments, the polyester has an M of 100,000 g / mol or less, 90,000 g / mol or less, or 80,000 g / mol or less. wIn some embodiments, the polyester has an M of 10,000 g / mol to 100,000 g / mol, 20,000 g / mol to 90,000 g / mol, or 30,000 g / mol to 80,000 g / mol. w The polyester M w can be measured using gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0097] In some embodiments, the polyester has a Tm of at least 250° C., preferably at least 260° C., more preferably at least 270° C., and most preferably at least 280° C. In some embodiments, the polyester polymer has a melting point of at most 350° C., preferably at most 340° C., more preferably at most 330° C., and most preferably at most 320° C. In some embodiments, the polyester has a Tm of 250° C.-350° C., 260° C.-340° C., 270° C.-330° C., or 280° C.-320° C.

[0098] The polyester can be produced by a known method.

[0099] Thermally conductive filler The polymer composition includes a thermally conductive filler. As used herein, a thermally conductive filler has a thermal conductivity of at least 0.5 W / (m·K), at least 2 W / (m·K), or at least 4 W / (m·K) as measured by ASTM E1461-13. Useful thermally conductive fillers include inorganic oxides and nitrides, including, but not limited to, aluminum oxide (alumina), zinc oxide, magnesium oxide, and silicon dioxide, boron nitride, aluminum nitride, and silicon nitride; metals and metal alloys; silicon carbide powder; zinc sulfide, magnesium carbonate, and calcium fluoride powder; and the like.

[0100] Preferably, the thermally conductive filler is selected from the group consisting of inorganic oxides or nitrides, more preferably, the thermally conductive filler is selected from magnesium oxide, zinc oxide, boron nitride, and combinations thereof, with boron nitride being particularly preferred in some embodiments.

[0101] In some embodiments, the polymer composition comprises at least 5 wt%, at least 10 wt%, or at least 15 wt% of the thermally conductive filler. In some embodiments, the polymer composition comprises no more than 50 wt%, no more than 45 wt%, or no more than 40 wt% of the thermally conductive filler. In some embodiments, the polymer composition comprises between 5 wt% and 50 wt%, or between 10 wt% and 45 wt%, or between 15 wt% and 40 wt% of the thermally conductive filler.

[0102] Conductive Carbon Fiber The polymer composition includes conductive carbon fibers, where the conductive carbon fibers have a resistivity of less than 20 μΩ·m, less than 10 μΩ·m, less than 5 μΩ·m, or less than 3 μΩ·m.

[0103] In some embodiments, the polymer composition comprises at least 5%, or at least 10%, or at least 15% by weight of conductive carbon fibers. In some embodiments, the polymer composition comprises no more than 40%, or no more than 35%, or no more than 30% by weight of conductive carbon fibers. In some embodiments, the polymer composition comprises between 5% and 40%, or between 10% and 35%, or between 15% and 30% by weight of conductive carbon fibers.

[0104] Carbon fibers are generally cylindrical and are characterized by a length (along the long axis of the carbon fiber) and a cross-sectional diameter perpendicular to the long axis (referred to simply as the diameter).

[0105] In some embodiments, the carbon fibers have an average length of at least 5 μm, at least 50 μm, at least 100 μm, at least 150 μm, or at least 175 μm. In some embodiments, the carbon fibers have an average length of 400 μm or less, 350 μm or less, 300 μm or less, 250 μm or less, or 225 μm or less. In some embodiments, the carbon fibers have an average length of 5 μm to 400 μm, 50 μm to 350 μm, 100 μm to 300 μm, 150 μm to 250 μm, or 175 μm to 225 μm.

[0106] In some embodiments, the carbon fibers have an average diameter of at least 1 μm, at least 5 μm, at least 7 μm, or at least 8 μm. In some embodiments, the carbon fibers have an average diameter of 20 μm or less, 15 μm or less, 13 μm or less, or 12 μm or less. In some embodiments, the carbon fibers have an average diameter of 1 μm to 20 μm, 5 μm to 15 μm, 7 μm to 13 μm, or 8 μm to 12 μm.

[0107] In some embodiments, the length of the carbon fibers is significantly greater than their diameter, hi some embodiments, the carbon fibers have an aspect ratio, defined as the average ratio of length ("L") to maximum diameter ("D") (L / D), of at least 5, at least 10, at least 15, at least 20, or at least 25, or at least 30, or at least 50.

[0108] Additives The polymer composition may also include one or more conventional additives commonly used in the art, such as plasticizers, colorants, pigments (e.g., black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g., linear low density polyethylene, calcium stearate, magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, and antioxidants. In this specification, thermally conductive fillers and conductive carbon fibers are excluded from the additives.

[0109] In embodiments including additives, the total concentration of additives is less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1% by weight.

[0110] Polymer Composition The polymer composition of the present invention comprises a thermoplastic polymer, a thermally conductive filler, and conductive carbon fibers, and, as previously mentioned, the polymer composition is substantially free of glass fibers.

[0111] In some embodiments, the weight ratio of the total weight of the conductive carbon fibers to the total weight of all non-thermoplastic polymer components in the polymer composition is 1:3.8 or less, or 1:3.7 or less, or 1:3.6 or less, or 1:3.5 or less, or 1:3.4 or less, or 1:3.3 or less, or 1:3.2 or less, or 1:3.1 or less, or 1:3.0 or less.

[0112] In some embodiments, the ratio of the total weight of the conductive carbon fibers to the total weight of all non-thermoplastic polymer components in the polymer composition is at least 1:1, or at least 1:1.1, or at least 1:1.2, or at least 1:1.3, or at least 1:1.4, or at least 1:1.5, or at least 1:1.6, or at least 1:1.7, or at least 1:1.8.

[0113] In some embodiments, the ratio of the total weight of the conductive carbon fibers to the total weight of all non-thermoplastic polymer components in the polymer composition is from 1:1.0 to 1:3.8, or from 1:1.1 to 1:3.7, or from 1:1.2 to 1:3.6, or from 1:1.3 to 1:3.5, or from 1:1.4 to 1:3.4, or from 1:1.5 to 1:3.3, or from 1:1.6 to 1:3.2, or from 1:1.7 to 1:3.1, or from 1:1.8 to 1:3.0.

[0114] As discussed above, the use of conductive carbon fibers can improve the thermal conductivity properties of a polymer composition without encountering the inherent limitations of attempting to achieve such improvements using only purely thermally conductive fillers. In some embodiments, the polymer composition exhibits an in-plane thermal conductivity of at least 7 W / (m·K), or at least 8 W / (m·K), or at least 9 W / (m·K), or at least 10 W / (m·K), or at least 11 W / (m·K), or at least 12 W / (m·K), or at least 13 W / (m·K). In other words, the polymer composition exhibits a thermal conductivity that is at least 1.5 times, or at least 2 times, or at least 2.5 times, or at least 3 times that of a similar polymer composition in which the conductive carbon fibers are replaced with glass fibers. The in-plane thermal conductivity can be measured by a flash method according to ASTM E1461-13 "Standard Test Method for Thermal Diffusivity by the Flash Method".

[0115] The improvement in thermal conductivity does not come at the expense of the electrical resistivity of the polymer composition. Instead, the resistivity of the polymer composition of the present invention is surprisingly and unexpectedly substantially maintained as compared to a similar polymer composition in which the conductive carbon fibers are replaced with glass fibers. In some embodiments, the polymer composition has a thermal conductivity of at least 10 9 Ω cm, or at least 10 10 Ω cm, or at least 10 11 Ω cm, or at least 10 12 Ω cm, or at least 10 13 Ω cm, or at least 10 14 Ω cm, or at least 10 15 Ω cm, or at least 10 16 In some embodiments, the polymer composition has a volume resistivity of 10 18 In some embodiments, the polymer composition has a volume resistivity of 10 9 Ω cm~10 18 Ω cm, 10 10 Ω cm~1018 Ω cm, 10 11 Ω cm~10 18 Ω cm, 10 12 Ω cm~10 18 Ω cm, 10 13 Ω cm~10 18 Ω cm, 10 14 Ω cm~10 18 Ω cm, 10 15 Ω cm~10 18 Ω cm, or 10 16 Ω cm~10 18 It has a volume resistivity of Ω·cm. Volume resistivity can be measured according to ASTM D257.

[0116] Even more surprising is the fact that the tensile and flexural moduli of the polymeric compositions including carbon fibers are increased compared to similar polymeric compositions in which the conductive carbon fibers are replaced with glass fibers. In some embodiments, the polymeric compositions have a flexural modulus of at least 25 GPa, at least 30 GPa, or at least 35 GPa. In some embodiments, the polymeric compositions have a flexural modulus of 55 GPa or less, 50 GPa or less, or 45 GPa or less. In some embodiments, the polymeric compositions have a flexural modulus of 25 GPa to 55 GPa, 30 GPa to 50 GPa, or 35 GPa to 45 GPa. In some embodiments, the polymeric compositions have a tensile modulus of at least 25 GPa, at least 30 GPa, or at least 35 GPa. In some embodiments, the polymeric compositions have a tensile modulus of 55 GPa or less, 50 GPa or less, or 45 GPa or less. In some embodiments, the polymeric compositions have a tensile modulus of 25 GPa to 55 GPa, 30 GPa to 50 GPa, or 35 GPa to 45 GPa.

[0117] In some embodiments, the polymer composition has only a single thermoplastic polymer and / or a single thermally conductive filler, in some such embodiments, the thermoplastic polymer is either polyphenylsulfide or polyphthalamide, and / or the thermally conductive filler is boron nitride.

[0118] Method for producing a polymer composition A method for making the polymer composition is also provided.

[0119] The polymer composition may be made by methods well known to those skilled in the art. For example, such methods include, but are not limited to, melt mixing processes. The melt mixing process is typically carried out by heating the polymer components above the glass transition temperature or melting temperature of the thermoplastic polymer. Suitable melt mixing devices are, for example, kneaders, Banbury mixers, single screw extruders, and twin screw extruders. Preferably, an extruder is used that is equipped with a means for feeding all of the desired components to the extruder, either to the throat or to the barrel of the extruder. The components may be fed simultaneously, i.e., as a dry blend of one or more powder granules, or may be fed separately.

[0120] The order of combining the components during melt mixing is not particularly limited. In one embodiment, the components can be mixed in a single batch, such that a desired amount of each component is added together and then mixed. In another embodiment, an initial subset of components can be mixed together first, and one or more remaining components can be added to the mixture for further mixing. For clarity, the entire desired amount of each component need not be mixed as a single amount. For example, for one or more components, a partial amount can be added and mixed first, followed by some or all of the remaining amount.

[0121] Shaped products and manufacturing methods Filaments and shaped articles comprising the polymer compositions of the present invention, as well as methods of making the filaments and shaped articles, are also provided.

[0122] The polymer compositions are well suited for the manufacture of articles useful in a variety of applications. For example, the polymer compositions of the present invention are believed to be particularly suited for use as functional or structural parts of i) electronic devices, ii) automobiles, iii) motors, iv) batteries, v) LEDs, vi) electronic boards, vii) electric vehicle charging stations, viii) vacuum or vacuum systems, and the like.

[0123] Shaped articles can be produced from the polymeric compositions using any suitable melt processing method, such as injection molding, extrusion, rotational molding, compression molding, or blow molding.

[0124] The shaped article can also be produced by additive manufacturing, where the shaped article is printed from a polymer composition.

[0125] Additive manufacturing systems are used to print or otherwise build a feature from a digital representation of the feature by one or more additive manufacturing techniques. Examples of commercially available additive manufacturing techniques include extrusion-based techniques, selective laser sintering, powder / binder jetting, electron beam melting, and stereolithography processes. For each of these techniques, the digital representation of the feature is first sliced ​​into multiple horizontal layers. For each layer, a tool path is then provided that instructs a particular additive manufacturing system to print the given layer.

[0126] For example, in an extrusion-based additive manufacturing system, a built article may be printed from a digital representation of the article layer-by-layer by extruding and abutting strips of a polymer composition. The polymer composition is extruded through an extrusion tip carried by the system's print head and deposited as a series of tracks onto a platen in the xy plane. The extruded material fuses with previously deposited material and solidifies as it cools. The position of the print head relative to the substrate is then incremented along the z-axis (perpendicular to the xy plane), and the process is repeated to form a built article that resembles the digital representation. An example of an extrusion-based additive manufacturing system is Fused Filament Fabrication ("FFF").

[0127] As another example, in powder-based additive manufacturing systems, a laser is used to locally sinter powder into a solid part. The part is produced by sequentially depositing layers of powder and subsequently sintering an image onto the layers with a laser pattern. An example of a powder-based additive manufacturing system is selective laser sintering ("SLS").

[0128] As another example, shaped articles can be manufactured using continuous fiber reinforced thermoplastic (FRTP) printing methods, which are based on fused deposition modeling and print a combination of fibers and resin.

[0129] Accordingly, some embodiments include a method for producing a shaped article comprising printing layers of a polymer composition to form the shaped article by an extrusion-based additive manufacturing system (e.g., FFF), a powder-based additive manufacturing system (e.g., SLS), or a FRTP printing method.

[0130] Some embodiments include a filament comprising the polymer composition. Preferably, the filament is suitable for use in an additive manufacturing method, such as FFF, as described above.

[0131] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that any term may be unclear, the statements of this application shall control.

[0132] Illustrative embodiments will now be described in the following non-limiting examples. EXAMPLES

[0133] The resistivity, thermal conductivity, and mechanical properties were evaluated for the various embodiments.

[0134] Starting materials RYTON® PPS manufactured by Solvay Specialty Polymers USA, LLC. Boron nitride manufactured by Momentive Performance Materials Inc. Zinc oxide (ZnO) manufactured by DreyTek, Inc. Magnesium oxide (MgO) manufactured by Ube Material Industries, Ltd. Fiberglass made by 3B - the fiberglass company. Carbon fiber made by Solvay Cytec. Mold release agent, HDPE6007G, from Nexeo Plastics.

[0135] Compounding of polymer composition Each formulation was melt compounded using a 26 mm diameter Coperion® ZSK-26 co-rotating partially intermeshing twin screw extruder with an L / D ratio of 48: 1. Barrel sections 2-12 and die were heated to set point temperatures as follows: Barrels 2-6: 300°C; Barrels 7-12: 300°C; Die: 300°C.

[0136] In each case, the thermoplastic polymer was fed at barrel section 1 using a gravimetric feeder at a throughput rate ranging from 30 to 35 pounds per hour. The extruder was operated at a screw speed of approximately 200 RPM. Vacuum was applied at barrel zone 10 using a vacuum level of approximately 27 inches of mercury. A single hole die was used for all of the polymer compositions to produce filaments approximately 2.6 to 2.7 mm in diameter, and the polymer filaments emerging from the die were quenched in water and fed into a pelletizer to produce pellets approximately 2.7 mm in length. The pellets were dried according to the test procedure applied to the samples before being injection molded into samples.

[0137] Electrical characteristics evaluation Volume resistivity was measured according to ASTM D257.

[0138] Mechanical property evaluation The following ISO test methods were used in evaluating the mechanical properties of the compounds: Tensile properties: ISO 527 Flexural properties ISO 178 The samples were prepared according to ISO procedures.

[0139] Thermal property evaluation The in-plane and perpendicular thermal conductivities were measured by a flash method in accordance with ASTM E1461-13 "Standard Test Method for Thermal Diffusivity by the Flash Method."

[0140] Experimental Results

[0141] [Table 1]

[0142] Table 1 shows the formulations that were prepared and the data obtained therefor. Surprisingly and unexpectedly, as also shown in Figure 1, the polymer compositions in which the glass fibers were replaced with carbon fibers (Inventive Examples E1-E4) exhibited in-plane thermal conductivity that was at least two times greater than the same compositions with glass fibers (Comparative Examples C1-C4). Increases in the transverse conductivity, tensile modulus, and flexural modulus were also observed.

[0143] Moreover, as shown in Table 1 and Figure 2, the polymeric compositions comprising carbon fibers and at least one thermally conductive filler, but substantially free of glass fibers (Inventive Examples E1-E3) exhibited these surprising results without substantial or any loss in volume resistivity compared to compositions without thermally conductive filler (Comparative Examples C5-C7) or without glass fibers (Comparative Examples C1-C4). This result is also surprising and unexpected.

Claims

1. A polymer composition comprising: - 25 to 50% by weight of a thermoplastic polymer; - 10 to 45% by weight of a thermally conductive filler; - 15 to 30% by weight of conductive carbon fibers; - less than 5% by weight of an additive; wherein the percentages by weight are based on the total weight of the polymer composition, and the polymer composition is substantially free of glass fibers polymer composition.

2. The polymer composition according to claim 1, wherein the ratio of the total weight of the conductive carbon fibers in the polymer composition to the total weight of all non-thermoplastic polymer components is less than 1:3.

8.

3. The polymer composition according to claim 1, wherein the thermally conductive filler is an inorganic oxide or an inorganic nitride.

4. The polymer composition according to claim 1, wherein the thermally conductive filler is boron nitride.

5. having a volume resistivity of at least 10 ９ Ω·cm as measured according to ASTM D257, the polymer composition according to claim 1.

6. The polymer composition according to claim 1, comprising a tensile modulus of at least 25 GPa, preferably at least 30 GPa, more preferably at least 35 GPa.

7. The polymer composition according to claim 1, comprising a flexural modulus of at least 25 GPa, preferably at least 30 GPa, more preferably at least 35 GPa.

8. The polymer composition according to claim 1, comprising an in-plane thermal conductivity of at least 7 W / (m·K), preferably at least 10 W / (m·K), even more preferably at least 12 W / (m·K), most preferably at least 13 W / (m·K).

9. The polymer composition according to claim 1, wherein the thermoplastic polymer is selected from the group consisting of poly(aryl sulfide), polyamide, poly(aryl ether sulfone), poly(aryl ether ketone), liquid crystal polymer, and polyester.

10. The polymer composition according to claim 1, wherein the thermoplastic polymer is poly(arylene sulfide).

11. The polymer composition according to claim 1, wherein the thermoplastic polymer is polyphenylene sulfide.

12. The polymer composition according to claim 1, wherein the thermoplastic polymer is polyamide.

13. An article comprising the polymer composition according to any one of claims 1 to 12.

14. The article according to claim 13, wherein the article is selected from the group consisting of an electronic device, an automobile, a motor, a battery, an LED, an electronic substrate, an electric vehicle charging station, a vacuum or a vacuum system, or a component of any of these.

Images