Thermally conductive polymer compositions and articles made therefrom - Patents.com

Abstract

Polymer compositions and articles made therefrom are provided. The polymer compositions include 25-50 wt.% thermoplastic polymer; 10-45 wt.% thermally conductive filler; 15-30 wt.% carbon fiber; 2-8 wt.% reinforcing agent; and less than 5 wt.% additives. The polymer compositions are substantially free of glass fibers. The polymer compositions described herein surprisingly exhibit significantly improved thermal conductivity compared to similar polymer compositions that do not include the reinforcing agent and / or in which carbon fibers are replaced with glass fibers.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 225,626, filed July 26, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] Polymer compositions are provided that are also thermally conductive while having advantageous mechanical properties. Articles made therefrom are also provided. In particular, the polymer compositions include a combination of a thermoplastic polymer and a thermally conductive filler with carbon fiber and a reinforcing agent. [Background technology]

[0003] Polymer compositions are used in many applications, such as motors, batteries, LEDs, electronic circuit boards, etc. In many of these, the polymer compositions desirably function to help dissipate heat from any heat-generating components. Polymer compositions used in such applications also desirably have mechanical properties and / or dimensional stability that allow them to perform consistently through multiple thermal cycles.

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

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

[0006] - 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; - 2-8% by weight of a reinforcing agent; - with less than 5% by weight of additives A polymer composition comprising: - weight percent is based on the total weight of the polymer composition; - the polymer composition is substantially free of glass fibers; - the through-plane thermal conductivity of the polymer composition is at least 1.5 W / (m K) A polymer composition is provided.

[0007] Also provided are articles comprising the polymer composition, for example selected from the group consisting of structural or functional parts such as i) electronic devices, ii) automobiles, iii) motors, iv) batteries, v) LEDs, vi) electronic boards, vii) electric vehicle charging stations, viii) vacuum or vacuum systems, etc. [Brief description of the drawings]

[0008] [Figure 1] 1 is a bar graph illustrating the in-plane thermal conductivity (W / m·K) of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Diagram 2] 1 is a bar graph illustrating the tensile modulus (GPa) of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Diagram 3] 1 is a bar graph illustrating the flexural modulus (GPa) of various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Figure 4] 1 is a bar graph illustrating the percent change in tensile break strain exhibited by formulations with toughening agent versus formulations without toughening agent for various comparative (C1-C3) and inventive (E1-E3) polymer compositions. [Diagram 5]1 is a bar graph illustrating the percent change in flexural break strain exhibited by formulations with toughening agent versus formulations without toughening agent for 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, carbon fiber and a reinforcing agent. Importantly, the polymer composition is substantially free of glass fiber. Surprisingly, it has been found that the polymer composition described herein has significantly improved thermal conductivity compared to a similar polymer composition without a reinforcing agent and / or a similar polymer composition in which carbon fiber is replaced with glass fiber. Furthermore, the elongation / strain at break of the polymer composition comprising carbon fiber and a reinforcing agent is increased while the tensile and flexural moduli of the polymer composition are substantially maintained compared to a similar polymer composition without a reinforcing agent.

[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 that is less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%. As used herein, weight percent is based on the total weight of the polymeric composition, unless otherwise specified.

[0011] As used herein, "substantially maintained" means indicating that the property changes by no more than 30%, no more than 20%, no more than 15%, no more than 10%, no more than 5%, or no more than 1% as compared to the property measured in a similar polymer composition without the toughening agent.

[0012] Any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Further, any element or component listed in a list of elements or components may be omitted from such list.

[0013] 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.

[0014] As used herein, the mole percentage of a particular repeat unit is determined relative to the total number of repeat units in the indicated polymer, unless otherwise specified.

[0015] The amount of energy in the form of heat required to bring about a change in state of a thermoplastic polymer from a solid to a liquid form is called the heat of fusion ("ΔH f "), and the temperature at which this change of state occurs is called the melting temperature (Tm). ΔH f and Tm can be measured according to ASTM D3418.

[0016] The glass transition temperature (Tg) is the temperature at which an amorphous material (or amorphous regions within a semicrystalline material) transitions from a hard and relatively brittle state to a viscous or rubbery state. Tg can be measured according to ASTM E1356, "Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry."

[0017] The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine.

[0018] Unless specifically limited otherwise, the terms "alkyl," as well as derivative 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.

[0019] Similarly, unless specifically stated 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." An aromatic group may be substituted with one or more C1-C6 alkyl groups, such as, for example, methyl or ethyl.

[0020] Aryl groups may also contain one or more heteroatoms, such as N, O, or S, and in such cases may be appropriately referred to as "heteroaryl" groups. Such heteroaromatic rings may also 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.

[0021] 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 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C15 aryloxy or C6-C15 aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied.

[0022] 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. Suitable thermoplastic polymers 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.

[0023] 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.

[0024] 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 the thermoplastic polymers is within the ranges given above.

[0025] In some embodiments, the thermoplastic polymer is semi-crystalline. As used herein, a semi-crystalline polymer has a heat of fusion ("ΔH") that is 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 (at a 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.

[0026] Poly(arylene sulfide) In some embodiments, the thermoplastic polymer is a poly(arylene sulfide) (PAS). As used herein, a poly(arylene sulfide) is defined as a polymer having at least 50 mol % of the formula (I): -[-Ar-S-]- (I) (wherein Ar is arylene). Repeating units (RPAS ) refers to any polymer containing

[0027] In some embodiments, the repeating unit (R PAS ) is a formula for the following group: [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, in each occurrence, is independently an integer from 0 to 4; - j, in each occurrence, is independently an integer from 0 to 3. is represented by a formula selected from:

[0028] Repeating unit (R PAS In the above 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.

[0029] In one embodiment, -Ar- in formula (I) is a phenyl group, such that the repeat unit (R PAS Preferably, -Ar- in formula (I) is represented by formula (II) where i is 0 and the phenylene moiety has a 1,4-bond to a moiety other than R, such that the repeat unit (R PAS ) has the following formula (II'): [ka] It is expressed as:

[0030] In such embodiments, the poly(arylene sulfide) is polyphenylene sulfide.

[0031] 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) is essentially made up of repeat units (R PAS In another embodiment, the repeat units (R PAS ) is 100 mole %, and in these embodiments, the poly(arylene sulfide) has a repeat unit (R PAS )

[0032] 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. wIn 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 by gel permeation chromatography ("GPC") using a 4-chloronaphthalene standard.

[0033] In some embodiments, the poly(arylene sulfide) has a melting temperature ("T") of at least 200°C, at least 220°C, at least 240°C, or at least 250°C. m In some embodiments, the poly(arylene sulfide) (PAS) has a T of 350° C. or less, 320° C. or less, 300° C. or less, or 285° C. or less. m In some embodiments, the poly(arylene sulfide) (PAS) has a T of 200° C. to 350° C., 220° C. to 320° C., 240° C. to 300° C., or 250° C. to 285° C. m has.

[0034] The melt flow rate (at 316° C. under a weight of 5 kg according to ASTM D1238, procedure B) of the poly(phenylene sulfide) (poly(arylene sulfide) according to formula (II′)) may be 50 to 400 g / 10 min, for example 60 to 300 g / 10 min or 70 to 200 g / 10 min.

[0035] The poly(arylene sulfides) and poly(phenylene sulfides) can be prepared by known methods.

[0036] polyamide In some embodiments, the thermoplastic polymer is a polyamide (PA). Polyamide refers to a polymer that includes at least 50 mol% of repeat units having at least one amide bond (-CONH-). In some embodiments, the polyamide has the formula (V): [ka] (In the formula, - R2 is a bond, C1~C 15 Alkyl and C6-C 30 aryl; - R3 is C1~C 20 Selected 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 are selected from the group consisting of halogen, hydroxyl (-OH), sulfo (-SO3H), C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy and C6-C 15 aryl) Repeating units (R PA ).

[0037] In some embodiments, R3 in formula (V) is phenyl and the polyamide has formula (VI): [ka] It is a polyphthalamide conforming to the above.

[0038] 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 PAIn such embodiments, the poly(arylene sulfide) essentially comprises repeat units (R PA In another embodiment, the polyamide comprises 100 mol % of the repeat units of formula (V) and / or (VI) (R PA According to such an embodiment, the polyamide comprises repeating units (R PA )

[0039] 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. w In some embodiments, the polyamide has an M of 150,000 g / mole or less, 100,000 g / mole or less, 90,000 g / mole or less, 85,000 g / mole or less, or 80,000 g / mole 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 by gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0040] 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.

[0041] The polyamides and polyphthalamides can be prepared by known methods.

[0042] Poly(aryl ether sulfone) In some embodiments, the thermoplastic polymer is a poly(aryl ether sulfone) (PAES). Poly(aryl ether sulfone)s include, but are not limited to, polysulfone, polyphenylsulfone, and polyethersulfone.

[0043] The poly(aryl ether sulfone) comprises at least 50 mol % of formula (VII): [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, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, 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 a group represented by formula (VIII) - C(R2)(R2)- (VIII) (In the formula, R2, in 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, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium. is selected from the group consisting of Repeating units (R PAES ) refers to any polymer containing

[0044] T is preferably a bond (i.e., the polyarylethersulfone is a polyphenylsulfone), a sulfone group (i.e., the polyaryleneethersulfone is a polyethersulfone) or a group according to formula (VIII) (i.e., the polyarylethersulfone is a polysulfone) where each R2 is a methyl group.

[0045] Repeating unit (R PAES 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.

[0046] 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) essentially consists of the repeating unit (R PAES In another embodiment, the poly(aryl ether sulfone) has 100 mol % of the repeating units consisting of the repeating unit (R PAES According to such an embodiment, the poly(aryl ether sulfone) is such that the repeating unit (R PAES )

[0047] The poly(aryl ether sulfone) may 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) may be measured 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.

[0048] 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. or less. 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.

[0049] The poly(aryl ether sulfone)s can be prepared by known methods.

[0050] 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, the polysulfone is at least 50 mol % of the compound of formula (VII-A): [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, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - i, for each R, is independently an integer from 0 to 4. Repeating units (R PSU ) refers to any polymer containing

[0051] In one embodiment, i is 0 for each R in formula (VII-A). According to this embodiment, the repeat unit (R PSU ) is represented by formula (VII-B): [ka] is a unit of.

[0052] Repeating unit (R PSU 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.

[0053] 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 (R PSU In such embodiments, the polysulfone essentially comprises repeat units (R PSUIn another embodiment, the polysulfone comprises 100 mol % of the repeating units of formula (VII-A) and / or (VII-B) (R PSU According to such an embodiment, the polysulfone comprises repeating units (R PSU )

[0054] 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 measured by gel permeation chromatography (GPC) using polystyrene standards and 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).

[0055] 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.

[0056] Polysulfones can be prepared by methods well known in the art.

[0057] 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, the polyphenylsulfone is at least 50 mol % of the compound of formula (VII-C): [ka] Repeating units (R PPSU ) refers to any polymer containing

[0058] 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 of the repeat units in the polyphenylsulfone are repeat units (R PPSU In such an embodiment, the polyphenylsulfone essentially consists of the repeating unit (R PPSU In another embodiment, the polyphenylsulfone comprises 100 mol % of the repeating units of the repeating unit (R PPSU According to such an embodiment, the polyphenylsulfone is such that the repeating unit (R PPSU )

[0059] 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 about 100,000 g / mol or less, or about 90,000 g / mol or less, or about 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, 30,000 g / mol to 90,000 g / mol, or 40,000 g / mol to 80,000 g / mol. w The polyphenylsulfone M w can be measured by gel permeation chromatography ("GPC") using polystyrene standards.

[0060] 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. or less. 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.

[0061] Polyphenylsulfone can be prepared by known methods.

[0062] 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, the polyether sulfone is at least 50 mol % of the compound of formula (VII-D): [ka] Repeating units (R PES ) refers to any polymer containing

[0063] 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 essentially consists of the repeating unit (R PES )

[0064] In another embodiment, the polyethersulfone has 100 mole % of the repeating units being the repeating units (R PES According to such an embodiment, the polyethersulfone is such that the repeating unit (R PES )

[0065] 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 by gel permeation chromatography ("GPC") using polystyrene standards.

[0066] 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.

[0067] Polyethersulfones can be prepared by known methods.

[0068] Poly(aryl ether ketone) (PAEK) In some embodiments, the thermoplastic polymer is a poly(aryl ether ketone) (PAEK).

[0069] Poly(aryl ether ketone)s are those having at least 50 mole % repeat units (R PAEK ) refers to any polymer containing

[0070] In this specification, the repeating unit (R PAEK ) is represented by formulas (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 metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; it is understood that each group that can be substituted can be substituted or unsubstituted, and if substituted, can include 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. is a repeating unit.

[0071] Repeating unit (R PAEK ), each phenylene moiety is independently a repeat unit (R PAEK ) may have 1,2-, 1,3-, or 1,4-bonds to other moieties other 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.

[0072] Repeating unit (R PAEK In some embodiments of formula (VIII)-(XI), i is 0 for each R. According to this embodiment, the repeat unit (R PAEK ) is represented by formulas (VIII-A) to (XI-A): [ka] It is expressed as:

[0073] At least 50% of the repeating units are repeating units (R PAEK ), are also understood by those skilled in the art to belong to the genus of poly(ether ether ketone) (PEEK).

[0074] According to an 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) essentially comprises repeat units (R PAEK )

[0075] In another embodiment, the poly(aryl ether ketone) has 100 mol % of the repeating units of formula (VIII), formula (IX), formula (X), and / or formula (XI) (R PAEK According to such an embodiment, the poly(aryl ether ketone) comprises repeat units (R PAEK )

[0076] 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, 50,000 g / mol to 150,000 g / mol. w has.

[0077] Poly(aryl ether ketone) M w can be measured by gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0078] 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. to 400° C., 280° C. to 390° C., 290° C. to 380° C., or 280° C. to 370° C. The poly(aryl ether ketones) and poly(ether ether ketones) can be prepared by known methods.

[0079] Liquid Crystal Polymer In some embodiments, the thermoplastic polymer is a liquid crystal polymer formed from the polycondensation of the following monomers: terephthalic acid, an aromatic diol, a first aromatic dicarboxylic acid different from terephthalic acid, and an aromatic hydroxycarboxylic acid.

[0080] In some embodiments, the aromatic diol has formula (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 15C6-C optionally substituted with one or more substituents selected from the group consisting of aryl 30 aryl groups; - T1 is a bond, O, S, -SO2-, -C(=O)-, and C1 to C 15 alkyl) is represented by a formula selected from:

[0081] 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.

[0082] In some embodiments, the first aromatic dicarboxylic acid is independently represented by formulae (XIV) and (XV): HOOC-Ar1-COOH (XIV) HOOC-Ar2-T2-Ar3-COOH (XV) wherein Ar1-Ar3 are as defined above and are independently selected; T2 is selected from the group consisting of a bond, O, and S. is represented by a formula selected from:

[0083] 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.

[0084] In some embodiments, the aromatic hydroxycarboxylic acid has the formula (XVI) and (XVII): HO-Ar1-COOH (XVI) HO-Ar2-Ar3-COOH (XVII) (wherein Ar1 to Ar3 are as defined above and are independently selected). is represented by a formula selected from:

[0085] 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.

[0086] As used herein, LCP is formed from the aforementioned monomers and contains at least 50% of the formulae (XVIII) to (XI): [ka] (wherein Ar1 to Ar3, T1 and T2 are as defined above and are independently selected). Repeating units (R LCP ) refers to any polymer having the

[0087] 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). Accordingly, the selection of Ar1 to Ar3, T1 and T2 for the monomers according to formulae (XII) to (XVII) also determines the repeat units R according to formulae (XIX) to (XIXV). LCP Preferably, the repeating unit R 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 has repeating units R according to the formulas (XXI) and (XXII) LCP is formed by polycondensation of isophthalic acid and has repeating units R according to the formulas (XXIII) and (XXIV) LCP is formed by polycondensation of 4-hydroxybenzoic acid.

[0088] In some embodiments, a repeat unit R according to formula (XVIII)-(XXIV) LCPis 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 99 mol%, or at least 99.9 mol%.

[0089] In some embodiments, a 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 %.

[0090] 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 hexafluoroisopropanol solvent and poly(methyl methacrylate) standards.

[0091] 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.

[0092] The liquid crystal polymer can be prepared by known methods.

[0093] polyester In some embodiments, the thermoplastic polymer is a polyester. As used herein, a polyester is defined as a polymer having at least 50 mol % repeat units (R PE In some embodiments, the polyester refers to any polymer comprising the formula (XXV): [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. Repeating units (R PE ).

[0094] Repeating unit (R PE 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.

[0095] In some embodiments, i and j are each zero, T is a bond, and / or n is 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).

[0096] 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 essentially consists of the repeating unit (R PE In another embodiment, the polyester comprises 100 mol % of the repeating units of the repeating unit (R PE According to such an embodiment, the polyester is such that the repeating unit (R PE )

[0097] 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 / mole or less, 90,000 g / mole or less, or 80,000 g / mole or less. w In some embodiments, the polyester has an M from 10,000 g / mol to 100,000 g / mol, from 20,000 g / mol to 90,000 g / mol, or from 30,000 g / mol to 80,000 g / mol. w The polyester M w can be measured by gel permeation chromatography ("GPC") using polymethyl methacrylate standards.

[0098] 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.

[0099] The polyesters can be prepared by known methods.

[0100] 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, but are not limited to, 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.

[0101] Preferably, the thermally conductive filler is selected from the group consisting of inorganic oxides or nitrides, and 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.

[0102] 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%, between 10 wt% and 45 wt%, or between 15 wt% and 40 wt% of the thermally conductive filler.

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

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

[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 the length to the longest diameter (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] Reinforcement The polymer composition comprises a toughening agent. The toughening agent is an amorphous polymer that generally has a low Tg, for example, below room temperature, below 0°C, or even below -25°C. As a result of its low Tg, the toughening agent is typically elastomeric at room temperature. The toughening agent can be a functionalized polymer backbone.

[0109] The polymer backbone of the toughening agent may be selected from elastomeric backbones comprising polyethylene and their copolymers, such as ethylene-butene, ethylene-octene; polypropylene and their copolymers; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene ethylene butadiene styrene (SEBS); block copolymer styrene butadiene styrene (SBS); core-shell elastomers of the methacrylate-butadiene-styrene (MBS) type, or mixtures of one or more of the above.

[0110] When the toughening agent is functionalized, backbone functionalization can occur by copolymerization of monomers containing the functionalization or by grafting the polymer backbone with additional components.

[0111] Specific examples of functionalized toughening agents are, among others, terpolymers of ethylene, acrylic esters, and glycidyl methacrylate, copolymers of ethylene, butyl acrylate, and glycidyl methacrylate, ethylene-maleic anhydride copolymers, EPR grafted with maleic anhydride, styrene copolymers grafted with maleic anhydride, SEBS copolymers grafted with maleic anhydride, styrene-acrylonitrile copolymers grafted with maleic anhydride, and ABS copolymers grafted with maleic anhydride. In some embodiments, the toughening agent is a terpolymer of ethylene, acrylic esters, and glycidyl methacrylate, copolymerate of ethylene, butyl acrylate, or copolymer of ethylene, butyl acrylate, and glycidyl methacrylate.

[0112] In some embodiments, the concentration of the toughening agent in the polymer composition is at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, or at least 2.5 wt%. In some embodiments, the concentration of the toughening agent in the polymer composition is 10 wt% or less, 9.5 wt% or less, 9 wt% or less, 8.5 wt% or less, or 8 wt% or less. In some embodiments, the concentration of the toughening agent in the polymer composition is 0.1 wt%-10 wt%, 0.5 wt%-9.5 wt%, 1 wt%-9 wt%, 1.5 wt%-8.5 wt%, or 2 wt%-8 wt%.

[0113] Additives The polymer composition may also include one or more 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 or magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, and antioxidants. As used herein, additives exclude thermally conductive fillers, carbon fibers, and reinforcing agents.

[0114] In embodiments including additives, the total additive concentration 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.

[0115] Polymer Composition The polymer composition includes a thermoplastic polymer, a thermally conductive filler, carbon fibers, and a reinforcing agent, and as previously mentioned, the polymer composition is substantially free of glass fibers.

[0116] In some embodiments, the weight ratio of the total weight of carbon fiber and reinforcing agent to the total weight of all non-thermoplastic polymer components in the polymer composition is 1:3.5 or less, 1:3.4 or less, 1:3.3 or less, or 1:3.2 or less.

[0117] In some embodiments, the ratio of the total weight of carbon fibers to the total weight of all non-thermoplastic polymer components in the polymer composition is at least 1:1, at least 1:1.1, at least 1:1.2, or at least 1:1.3.

[0118] In some embodiments, the ratio of the total weight of carbon fiber to the total weight of all non-thermoplastic polymer components in the polymer composition is from 1:1.0 to 1:3.5, from 1:1.1 to 1:3.4, from 1:1.2 to 1:3.3, or from 1:1.3 to 1:3.2.

[0119] As noted above, the combination of carbon fibers and reinforcing agents provides a surprising improvement in the through-plane thermal conductivity of the polymer composition compared to a similar polymer composition without the reinforcing agent and / or in which the carbon fibers are replaced with glass fibers. This result is particularly surprising since reinforcing agents are understood by those skilled in the art to be amorphous and to reduce thermal conductivity. In some embodiments, the polymer composition exhibits a through-plane thermal conductivity of at least 1.5 W / (m·K), at least 1.75 W / (m·K), at least 2 W / (m·K), at least 2.25 W / (m·K), at least 2.5 W / (m·K), at least 2.75 W / (m·K), at least 3 W / (m·K), at least 3.25 W / (m·K), or at least 3.5 W / (m·K). In some embodiments, the polymeric composition exhibits an increase in through-plane thermal conductivity of at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, or at least 70% over the thermal conductivity of a similar polymeric composition containing carbon fiber but without the reinforcing agent. Through-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."

[0120] The thermal conductivity improvement does not come at the expense of the elongation of the polymer composition, which is surprisingly and unexpectedly increased compared to a similar polymer composition that includes carbon fiber but does not include a reinforcement. In some embodiments, the elongation of the polymer composition, measured as either tensile or flexural strain at break, is increased by at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or even 100% compared to a similar polymer composition that includes carbon fiber but does not include a reinforcement. In some embodiments, the elongation of the polymer composition that includes carbon fiber and a reinforcement is increased by more than 100%, or more than two times, compared to the elongation of a similar polymer composition that includes carbon fiber but does not include a reinforcement.

[0121] Even more surprising is the fact that the tensile and flexural moduli of the polymeric composition comprising carbon fiber and a reinforcement agent are substantially maintained as compared to a similar polymeric composition comprising carbon fiber but without a reinforcement agent, hi some embodiments, the tensile and flexural moduli of the polymeric composition are within 30%, within 20%, within 15%, within 10%, within 5%, or within 1% of the properties measured in a similar polymeric composition comprising carbon fiber but without a reinforcement agent.

[0122] In some embodiments, the polymer composition has only one thermoplastic polymer and / or only one thermally conductive filler, hi some such embodiments, the thermoplastic polymer is either polyphenylsulfide or polyphthalamide, and / or the thermally conductive filler is boron nitride.

[0123] Method for producing a polymer composition A method for making the polymer composition is also provided.

[0124] The polymer composition can be produced 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 the desired components into the extruder, either into the extruder throat or into the barrel. The components may be fed simultaneously, i.e., as a dry blend of one or more powder granules, or fed separately.

[0125] 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 the desired amount of each component is added together and then mixed. In another embodiment, a first 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, and then some or all of the remaining amount can be added and mixed.

[0126] Shaped products and manufacturing methods Filaments and shaped articles comprising the polymer compositions and methods of making the filaments and shaped articles are also provided.

[0127] The polymer compositions are suitable for the manufacture of articles useful in a wide variety of applications. For example, the polymer compositions may be particularly suitable for use as functional or structural components in 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.

[0128] Shaped articles may be produced from the polymeric compositions using any suitable melt processing method, such as injection molding, extrusion, rotational molding, compression molding, or blow molding.

[0129] The shaped article can also be produced by additive manufacturing, where the shaped article is printed from a polymer composition.

[0130] 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 a number of horizontal layers. For each layer, a tool path is then generated, which provides instructions to a particular additive manufacturing system for printing a given layer.

[0131] 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").

[0132] As another example, in powder-based additive manufacturing systems, a laser is used to locally sinter powder into a solid part. A built 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").

[0133] As another example, shaped articles can be prepared using a continuous fiber reinforced thermoplastic (FRTP) printing method, which is based on thermal lamination modeling and prints a combination of fibers and resins.

[0134] 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 continuous FRTP printing process.

[0135] 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.

[0136] 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 a term may be unclear, the statements of this application shall control.

[0137] Exemplary embodiments will now be described in the following non-limiting examples. EXAMPLES

[0138] Thermal conductivity and mechanical properties were evaluated for various embodiments.

[0139] 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. A strengthening agent manufactured by Sumitomo Chemical Co., Ltd. Mold release agent, HDPE 6007G, from Nexeo Plastics.

[0140] Formulation of the 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 the die were heated to set point temperatures as follows: Barrels 2-6: 300°C; Barrels 7-12: 300°C; Die: 300°C.

[0141] In each case, the thermoplastic polymer was fed in 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 in barrel zone 10 at 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 and then injection molded into samples according to the test procedure applied to the samples.

[0142] 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

[0143] The samples were prepared according to ISO procedures.

[0144] Thermal property evaluation Through-plane thermal conductivity was measured by the Flash method according to ASTM E1461-13, "Standard Test Method for Thermal Diffusivity by the Flash Method."

[0145] Experimental Results

[0146] [Table 1]

[0147] Table 1 shows the formulations that were prepared and the data obtained therefor. Surprisingly and unexpectedly, and as shown in Figure 1, polymer compositions containing reinforcement and in which glass fibers were replaced with carbon fibers (Invention Examples E1-E4) exhibited increased through-plane thermal conductivity compared to the same compositions with glass fibers (Comparative Examples C1-C4). As shown in Figures 2 and 3, the tensile and flexural moduli were substantially maintained.

[0148] Moreover, the polymer compositions of the present invention (E1-E4) exhibited these surprising results while also exhibiting increased elongation (tensile and flexural strain at break %) compared to the same compositions without reinforcement (C3, C6, C9, and C11, respectively). Even more surprisingly, and as shown in Figures 4 and 5, these increases in elongation were substantially greater than those seen between similar comparative samples, i.e., samples with glass fibers and no reinforcement (C1, C4, and C7) and samples with glass fibers along with reinforcement (C2, C5, and C8).

Claims

1. 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 carbon fiber; 2 to 8% by weight of a strengthening agent; less than 5% by weight of an additive and a polymer composition comprising, where the percentages by weight are based on the total weight of the polymer composition, the polymer composition substantially does not contain glass fiber, the through-plane thermal conductivity of the polymer composition is at least 1.5 W / (m·K), polymer composition.

2. The through-plane thermal conductivity of the polymer composition is at least 2 W / (m·K), the polymer composition according to Claim 1.

3. The through-plane thermal conductivity of the polymer composition is at least 2.25 W / (m·K), the polymer composition according to Claim 1.

4. The through-plane thermal conductivity of the polymer composition is at least 40% greater than that of a similar polymer composition without the strengthening agent, the polymer composition according to Claim 1.

5. The thermally conductive filler is an inorganic oxide or an inorganic nitride, the polymer composition according to Claim 1.

6. The thermally conductive filler is boron nitride, the polymer composition according to Claim 1.

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

8. The thermoplastic polymer is poly(arylene sulfide), the polymer composition according to Claim 1.

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

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

11. The polymer composition according to claim 1, wherein the reinforcing agent is selected from functionalized polymer skeletons.

12. The polymer composition according to claim 11, wherein the polymer skeleton of the reinforcing agent is selected from polyethylene and its copolymers; polybutene; polyisoprene; ethylene-propylene rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene ethylene butadiene styrene (SEBS); block copolymer styrene butadiene styrene (SBS); methacrylate-butadiene-styrene (MBS) type core-shell elastomer, or an elastomer skeleton containing one or more of the above mixtures.

13. The polymer composition according to claim 11, wherein the reinforcing agent is a functionalized reinforcing agent selected from the group consisting of a terpolymer of ethylene, an acrylic ester and glycidyl methacrylate, a copolymer of ethylene and butyl acrylate; a copolymer of ethylene, butyl acrylate and glycidyl methacrylate; an ethylene-maleic anhydride copolymer; EPR grafted with maleic anhydride; a styrene copolymer grafted with maleic anhydride; an SEBS copolymer grafted with maleic anhydride; a styrene-acrylonitrile copolymer grafted with maleic anhydride; an ABS copolymer grafted with maleic anhydride.

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

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

Images