Thermally conductive and electrically insulating compositions based on highly filled pbt with improved ductility and cti properties

Abstract

A thermoplastic composition includes: (a) about 10 wt% to about 40 wt% of a PBT (polybutylene terephthalate) component; (b) about 5 wt% to less than 10 wt% of a glass fiber component; (c) about 50 wt% to about 70 wt% of a mineral filler component including aluminum silicate, aluminum oxide, magnesium oxide, or a combination thereof; (d) about 0.1 wt% to about 10 wt% of an impact modifier component including about 0.4 wt% to about 3.5 wt% of an ethylene-ethyl acrylate copolymer (EEA) and about 0.5 wt% to about 3 wt% of an ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA); and optionally a polycarbonate-silicone copolymer component. The composition does not include a polycarbonate copolymer other than the optional polycarbonate-silicone copolymer in element (e). The composition has a comparative tracking index (CTI) rating of PLC-0 as determined according to UL746A.

Description

Technical Field

[0001] This disclosure relates to polybutylene terephthalate (PBT) thermoplastic compositions, and more particularly to PBT compositions comprising an impact modifier component, said PBT compositions having good ductility and comparative tracking index (CTI) characteristics. Background Technology

[0002] The demand for thermally conductive and electrically insulating polymer composites is growing. Polymers are thermal and electrical insulators, and therefore, to meet these properties, they can be formulated with high volumetric filler contents. However, high filler contents can adversely affect other properties, such as mechanical properties and processability, thus requiring formulation optimization. Formulating PBT-based compositions with optimized properties is a challenge.

[0003] In automotive applications, such as radar housings and high-voltage connectors, components are exposed to harsh operating conditions, including vibration loads, temperature rises due to the use of multiple processors, and other external forces during operation. Therefore, components in these applications should possess good mechanical properties, such as ductility, shock resistance, stiffness, and high thermal conductivity. Additionally, materials used in high-voltage charging systems (connectors, cables, and insulation) should have a high comparative tracking index (CTI).

[0004] These and other disadvantages are addressed through various aspects of this disclosure. Summary of the Invention

[0005] This disclosure relates to thermoplastic compositions comprising: (a) about 10 wt% to about 40 wt% of a PBT (polybutylene terephthalate) component; (b) about 5 wt% to less than 10 wt% of a glass fiber component; (c) about 50 wt% to about 70 wt% of a mineral filler component, said mineral filler component comprising aluminum silicate, alumina, magnesium oxide, or combinations thereof; (d) about 0.1 wt% to about 10 wt% of an impact modifier component, said impact modifier component comprising about 0.4 wt% to about 3.5 wt% of an ethylene-ethyl acrylate copolymer (EEA) and about 0.5 wt% to about 3 wt% of an ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA); and optionally a polycarbonate-siloxane copolymer component. The combined weight percentage of all components does not exceed 100 wt%, and all weight percentages are based on the total weight of the composition. The composition does not include any polycarbonate copolymers other than the optional polycarbonate-siloxane copolymers described in element (e). The composition has a Comparative Tracking Index (CTI) rating of PLC-0 as determined according to UL746A. Detailed Implementation

[0006] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of this disclosure, it should be understood that, unless otherwise specified, they are not limited to specific synthetic methods, or, unless otherwise specified, are not limited to specific reagents, and therefore they are subject to change. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0007] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from supplementary claims attached to the same independent claim.

[0008] Furthermore, it should be understood that, unless otherwise expressly stated, any method described herein is not intended to be construed as requiring its steps to be performed in a specific order. Therefore, in no way is an order intended to be inferred unless a method claim actually describes the order in which its steps are followed, or unless the claims or description specifically state that the steps are limited to a specific order. This applies to any possible non-expressive basis for interpretation, including: matters concerning the logic of the arrangement of steps or the flow of operations, the general meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the description.

[0009] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with the cited publications.

[0010] definition

[0011] It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. As used in the specification and claims, the term "comprising" can include aspects "consisting of" and "consisting essentially of". Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Reference will be made to numerous terms that should be defined herein in this specification and the following claims.

[0012] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” include plural indicators unless the context clearly specifies otherwise. Thus, for example, references to “PBT component” include mixtures of two or more PBT polymers.

[0013] As used herein, the term "composite" includes blends, mixtures, alloys, reaction products, etc.

[0014] A range may be expressed herein as a range from one value (first value) to another value (second value). When expressing such a range, the range includes, in some respects, one or both of the first and second values. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that a particular value forms another aspect. It should be further understood that the endpoints of each range are significant relative to and independent of the other endpoint. It should also be understood that many values ​​are disclosed herein, and each value is disclosed herein as “about” the particular value in addition to the value itself. For example, if the value “10” is disclosed, “about 10” is also disclosed. It should also be understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, 11, 12, 13, and 14 are also disclosed.

[0015] As used herein, the terms “about” and “at or about” mean that the quantity or value discussed may be a specific value, an approximate specific value, or about the same as the specific value. It should generally be understood that, as used herein, nominal values ​​indicate a variation of ±10%, unless otherwise indicated or inferred. These terms are intended to convey that similar values ​​promote equivalent results or effects as described in the claims. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be precise, but may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, quantities, sizes, formulations, parameters, or other quantities or characteristics are “about” or “approximate,” whether explicitly stated or not. It should be understood that where “about” is used before a quantifiable value, the parameter also includes the specific quantifiable value itself, unless otherwise specifically stated.

[0016] The components used to prepare the compositions of this disclosure and the compositions themselves used in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that while specific references to every individual and collective combination and arrangement of these materials cannot be explicitly disclosed, each is specifically considered and described herein. For example, if a particular compound is disclosed and discussed, and various modifications that may be made to multiple molecules comprising the compound are discussed, then every combination and arrangement and possible modifications of the compound is specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of the combination molecule AD is disclosed, then each combination is contemplated individually and collectively, even if each combination is not described separately; this means that combinations AE, AF, BD, BE, BF, CD, CE, and CF are considered disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including but not limited to the steps in methods of making and using the compositions of this disclosure. Therefore, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed in any specific aspect or combination of aspects of the method disclosed herein.

[0017] References to the weight parts of a particular element or component in the composition or article in the specification and the final claims indicate the weight relationship between the element or component and any other element or component, expressed as parts by weight. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and are present in such a ratio regardless of whether the compound contains other components.

[0018] Unless specifically stated to the contrary, the weight percentage of a component is based on the total weight of the formulation or composition including the component.

[0019] As used herein, the term "number-average molecular weight" or "M" refers to... n "These terms can be used interchangeably, and refer to the statistical average molecular weight of all polymer chains in the sample, defined by the following formula:"

[0020] ,

[0021] Where M i It is the molecular weight of the chain, and N iThis refers to the number of chains in the molecular weight range. For polymers, such as polycarbonate polymers, M can be determined using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards, by methods well known to those skilled in the art. n .

[0022] As used herein, the term "weight-average molecular weight" or "M" refers to... w "They can be used interchangeably and are defined by the following formula:

[0023] ,

[0024] Where M i It is the molecular weight of the chain, and N i This is the number of chains representing the molecular weight. (M) n In comparison, M w The molecular weight of a given chain is considered when determining its contribution to the average molecular weight. Therefore, the larger the molecular weight of a given chain, the greater its contribution to M. w The greater the contribution, the better. For polymers, such as polycarbonate polymers, M can be determined using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards, by methods known to those skilled in the art. w .

[0025] As used herein, the terms “polydispersity index” or “PDI” are used interchangeably and are defined by the following formula:

[0026] .

[0027] PDI has a value equal to or greater than 1, but when the polymer chains are close to a uniform chain length, PDI approaches one.

[0028] As used herein, the interchangeable terms “BisA,” “BPA,” or “bisphenol A” refer to compounds having a structure represented by the following formula:

[0029]

[0030] BisA can also be referred to by the names 4,4'-(propane-2,2-diyl)diol; p,p'-isopropylidene bisphenol; or 2,2-bis(4-hydroxyphenyl)propane. The CAS number for BisA is 80-05-7.

[0031] As used herein, “polycarbonate” refers to an oligomer or polymer comprising residues of one or more dihydroxy compounds (e.g., dihydroxy aromatic compounds) linked by carbonate bonds; it also encompasses homopolymers, copolymers, and (co)polyesters.

[0032] The terms “residue” and “structural unit” used to describe the composition of the polymer are synonymous throughout the specification.

[0033] As used herein, unless otherwise specified, the terms "weight percentage," "wt%," and "wt.%" are used interchangeably to indicate the weight percentage of a given component based on the total weight of the composition. That is, unless otherwise specified, all wt% values ​​are based on the total weight of the composition. It should be understood that the sum of the wt% values ​​of all components in the disclosed composition or formulation is equal to 100.

[0034] Unless otherwise stated herein, all testing standards are current and valid at the time of filing of this application.

[0035] Each raw material used in the example and / or comparative compositions described herein is commercially available and / or its manufacturing method is known to those skilled in the art.

[0036] It should be understood that the compositions disclosed herein have certain functions. This document discloses certain structural requirements for performing the disclosed functions, and it should be understood that various structures exist that can perform the same functions associated with the disclosed structures, and these structures generally achieve the same results.

[0037] thermoplastic composition

[0038] This disclosure relates to thermoplastic compositions comprising: (a) about 10 wt% to about 40 wt% of a PBT (polybutylene terephthalate) component; (b) about 5 wt% to less than 10 wt% of a glass fiber component; (c) about 30 wt% to about 75 wt% of a mineral filler component, said mineral filler component comprising aluminum silicate, alumina, magnesium oxide, or combinations thereof; (d) about 0.1 wt% to about 10 wt% of an impact modifier component, said impact modifier component comprising ethylene-ethyl acrylate copolymer (EEA) and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA); and optionally a polycarbonate-siloxane copolymer component. The combined weight percentage of all components does not exceed 100 wt%, and all weight percentages are based on the total weight of the composition. The composition does not include polycarbonate copolymers other than the optional polycarbonate-siloxane copolymer described in element (e).

[0039] As used herein, "polybutylene terephthalate" is a polyester that is interchangeable with poly(1,4-butylene terephthalate). Polybutylene terephthalate is a type of polyester. PBT components may include PBT homopolymers, PBT copolymers, or combinations thereof.

[0040] Specifically, the polymer component is chemically recycled poly(butylene terephthalate), named iQ PBT, derived from chemically upgraded recycled (or post-consumer recycled) PET. Fibers formed from iQ PBT offer environmental advantages and provide the desired modulus of elasticity, breaking stress, and elongation at break.

[0041] Commercial examples of upgraded recycled PBT include ELCRIN manufactured by SABIC™ Corporation. TM iQ resin PBT. PBT can be obtained from a poly(ethylene terephthalate) component by any method involving depolymerizing the poly(ethylene terephthalate) component and polymerizing the depolymerized poly(ethylene terephthalate) component with 1,4-butanediol to provide PET-derived PBT. For example, a PET-derived poly(butylene terephthalate) component can be prepared by a process involving depolymerizing poly(ethylene terephthalate) and / or poly(ethylene terephthalate) copolymers with a 1,4-butanediol component at a temperature of 180°C to 230°C, under stirring, in the presence of a catalyst component, at a pressure of at least atmospheric pressure, at elevated temperatures, and in an inert atmosphere to produce a melt mixture containing: oligomers containing a ethylene terephthalate moiety and oligomers containing a ethylene isophthalate moiety. The following are provided: oligomers containing diethylene terephthalate moieties, oligomers containing diethylene isophthalate moieties, oligomers containing butylene terephthalate moieties, oligomers containing butylene isophthalate moieties, covalently bonded oligomer moieties containing at least two of the above moieties, 1,4-butanediol, ethylene glycol, or combinations thereof; and the mixture is stirred and melted under subatmospheric pressure, and the temperature of the melt mixture is increased to an elevated temperature under conditions sufficient to form PET-derived PBT containing at least one residue derived from the poly(ethylene terephthalate) component.

[0042] In some respects, the PBT composition includes high-flow PBT with an intrinsic viscosity of less than 1.0 dL / g and low-flow PBT with an intrinsic viscosity of at least 1.0 dL / g. The intrinsic viscosity can be measured according to ASTM D2857 in a 60:40 phenol / tetrachloroethane mixture. In some respects, the intrinsic viscosity of high-flow PBT is less than 0.95 dL / g, or less than 0.9 dL / g, or less than 0.85 dL / g, or less than 0.8 dL / g, or less than 0.75 dL / g, or less than 0.7 dL / g, or about 0.66 dL / g. In other respects, the intrinsic viscosity of low-flow PBT is at least 1.05 dL / g, or at least 1.10 dL / g, or at least 1.15 dL / g, or about 1.2 dL / g.

[0043] In a specific aspect, the composition comprises high-flow PBT (e.g., PBT195) and low-flow PBT (e.g., PBT315) in ratios from 100:1 (100:1) to 1:2 (1:2), such as, but not limited to, 100:1 (high-flow PBT to low-flow PBT), 95:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, etc. 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 0.9:1, 0.8:1, 0.7:1, 0.6:1, 0.5:1, 0.4:1, 0.3:1, 0.2:1, 0.1:1, 0.05:1, or 0.01:1. Ranges selected from these ratios are also possible. Specifically, the composition comprises high-flow PBT and does not comprise low-flow PBT (e.g., 100% high-flow PBT).

[0044] The compositions according to various aspects of this disclosure comprise about 10 wt% to about 40 wt% of PBT components. In some aspects, the composition comprises at least 10 wt%, or at least 11 wt%, or at least 12 wt%, or at least 13 wt%, or at least 14 wt%, or at least 15 wt%, or at least 16 wt%, or at least 17 wt%, or at least 18 wt%, or at least 19 wt%, or at least 20 wt%, or at least 21 wt%, or at least 22 wt%, or at least 23 wt%, or at least 24 wt%, or at least 25 wt%, or at least 26 wt%, or at least 27 wt%, or at least 28 wt%, or at least 29 wt%, or at least 30 wt%, or at least 31 wt%, or at least 32 wt%, or at least 33 wt%, or at least 34 wt%, or at least 35 wt%, or up to 40 wt%, or up to 39 wt%, or up to 38 wt%, or up to 37 wt%, or up to 36 wt%, or up to 35 wt%, or up to 34 wt%, or up to 33 wt%. PBT components of wt%, or up to 32 wt%, or up to 31 wt%, or up to 30 wt%, or up to 29 wt%, or up to 28 wt%, or up to 27 wt%, or up to 26 wt%, or up to 25 wt%, or up to 24 wt%, or up to 23 wt%.

[0045] In some aspects, the thermoplastic composition includes about 5 wt% to less than 10 wt% of a glass fiber component. The glass fiber may be selected from E-type glass, S-type glass, AR-type glass, T-type glass, D-type glass, and R-type glass. In still other aspects, the glass fiber is selected from E-type glass, S-type glass, and combinations thereof. In still other aspects, the glass fiber is one or more S-type glass materials. High-strength glass is commonly referred to as S-type glass in the United States, R-type glass in Europe, and T-type glass in Japan. S-type glass was initially developed in the 1960s for military applications, and a lower-cost version, S-2 glass, was later developed for commercial applications. High-strength glass has significantly higher contents of silica, alumina, and magnesium oxide than E-type glass. S-2 glass is approximately 40%–70% stronger than E-type glass. Glass fibers can be produced by standard methods, such as steam or air blowing, flame blowing, and mechanical drawing. Exemplary glass fibers used in the thermoplastic compositions of this disclosure can be produced by mechanical drawing.

[0046] Glass fibers can be sized or unsized. Sizing glass fibers have a sizing composition, selected to be compatible with the polymer base resin, coated on their surface. The sizing composition promotes the impregnation and permeation of the polymer resin onto the fiber bundles and helps to achieve the desired physical properties in the thermoplastic composition.

[0047] In various other aspects, the glass fibers are sizing with a coating agent. In other aspects, the coating agent is present in an amount of about 0.1 wt% to about 5 wt% based on the weight of the glass fibers. In still other aspects, the coating agent is present in an amount of about 0.1 wt% to about 2 wt% based on the weight of the glass fibers.

[0048] In the preparation of glass fibers, numerous filaments can be formed simultaneously, sized with a coating agent, and then bundled into what is known as a strand. Alternatively, the strand itself can be formed first from the filaments and then sized. The amount of sizing used is typically sufficient to bond the glass filaments into a continuous strand, and ranges from about 0.1 wt% to about 5 wt% or from about 0.1 wt% to 2 wt% based on the weight of the glass fibers. Typically, this can be about 1.0 wt% based on the weight of the glass filaments.

[0049] In another aspect, the glass fibers can be continuous or chopped. In yet another aspect, the glass fibers are continuous. In yet another aspect, the glass fibers are chopped. The length of chopped strands of glass fibers can be from about 0.3 mm to about 10 cm, specifically from about 0.5 mm to about 5 cm, and more specifically from about 1.0 mm to about 2.5 cm. In various other aspects, the length of the glass fibers is from about 0.2 mm to about 20 mm. In yet another aspect, the length of the glass fibers is from about 0.2 mm to about 10 mm. In even another aspect, the length of the glass fibers is from about 0.7 mm to about 7 mm. In this field, when thermoplastic resin and glass fibers are reinforced in the form of composites, fibers with a length of about 0.4 mm are generally referred to as long fibers, and shorter fibers are referred to as short fibers. In yet another aspect, the length of the glass fibers can be 1 mm or longer. In yet another aspect, the length of the glass fibers can be 2 mm or longer.

[0050] In various other aspects, the glass fibers have a circular (or annular), flat, or irregular cross-section. Therefore, it is possible to use non-circular fiber cross-sections. In yet another aspect, the glass fibers have a circular cross-section. In yet another aspect, the diameter of the glass fibers is from about 1 µm to about 15 µm. In even another aspect, the diameter of the glass fibers is from about 4 µm to about 10 µm. In yet another aspect, the diameter of the glass fibers is from about 1 µm to about 10 µm. In yet another aspect, the diameter of the glass fibers is from about 7 µm to about 10 µm.

[0051] In some respects, glass fibers are bonded or unbonded glass fibers. Specifically, glass fibers are unbonded glass fibers. The term "unbonded" means that the glass fiber does not adhere to the polymeric components in the PBT composition, while "bonded" glass fibers are firmly adhered to the polymeric components. The unbonded / bonded properties of glass fibers can be controlled, for example, by coating the glass fiber with coatings such as epoxy, polyvinyl acetate, specific polyester resins, starch, acrylic resins, melamine, polyvinyl chloride, polyethylene oxide, polyurethane, or polyvinyl alcohol, or by using silane coupling agents, to modify the bonding characteristics between the glass fiber and other polymeric components in the PBT composition. In some respects, unbonded glass fibers provide improved impact strength compared to bonded or ground glass fibers.

[0052] In some respects, the thermoplastic composition comprises at least 5 wt%, or at least 5.5 wt%, or at least 6 wt%, or at least 6.5 wt%, or at least 7 wt%, or at least 7.5 wt%, or at least 8 wt%, or at least 8.5 wt%, or at least 9 wt%, or at most 10 wt%, or at most 9.5 wt%, or at most 9 wt%, or at most 8.5 wt%, or at most 8 wt%, or at most 7.5 wt% of glass fiber component.

[0053] The compositions according to various aspects of this disclosure comprise about 30 wt% to about 75 wt% of a mineral filler component, said mineral filler component comprising aluminum silicate, alumina, magnesium oxide, or combinations thereof. In some aspects, the compositions comprise at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt%, or at least 50 wt%, or at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at most 75 wt%, or at most 70 wt%, or at most 65 wt%, or at most 60 wt%, or at most 55 wt% of a mineral filler component.

[0054] In another aspect, the composition includes about 0.1 wt% to about 10 wt% of an impact modifier component, said impact modifier component comprising ethylene-ethyl acrylate copolymer (EEA) and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA). An exemplary EEA copolymer is ELVALOY™ AC 2615 acrylate copolymer, available from DuPont Performance Materials. An exemplary EMAGMA copolymer is Lotader® AX8900, available from SK Functional Polymer.

[0055] In some aspects, the composition comprises at least 0.1 wt%, or at least 0.2 wt%, or at least 0.3 wt%, or at least 0.4 wt%, or at least 0.5 wt%, or at least 0.6 wt%, or at least 0.7 wt%, or at least 0.8 wt%, or at least 0.9 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or at least 2.5 wt%, or at least 3 wt%, or at least 3.5 wt%, or at least 4 wt%, or at least 4.5 wt%, or at least 5 wt%, or up to 10 wt%, or up to 9.5 wt%, or up to 9 wt%, or up to 8.5 wt%, or up to 8 wt%, or up to 7.5 wt%, or up to 7 wt%, or up to 6.5 wt%, or up to 6 wt%, or up to 5.5 wt%, or up to 5 wt%, or up to 4.5 wt%, or up to 4 wt%, or up to 3.5 wt%. Impact modifier components of wt%, or up to 3wt%, or up to 2.5wt%, or up to 2wt%, or up to 1.5wt%, or up to 1wt%.

[0056] In a specific aspect, the composition comprises about 0.4 wt% to about 3.5 wt% of an EEA impact modifier. In another aspect, the composition comprises up to 3.5 wt%, or up to 3 wt%, or up to 2.5 wt%, or up to 2 wt%, or up to 1.5 wt%, or up to 1 wt% of an EEA impact modifier.

[0057] In some aspects, the composition comprises about 0.5 wt% to about 3 wt% of an EMAGMA impact modifier. In other aspects, the composition comprises up to 3 wt%, or up to 2.5 wt%, or up to 20 wt%, or up to 1.5 wt% of an EMAGMA impact modifier.

[0058] In some aspects, the impact modifier component further comprises 0.1 wt% to about 9 wt% of a polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier. An exemplary polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier is Hytrel®, available from DuPont. In a specific aspect, the composition comprises up to 9 wt%, or up to 8.5 wt%, or up to 8 wt%, or up to 7.5 wt%, or up to 7 wt%, or up to 6.5 wt%, or up to 6 wt%, or up to 5.5 wt%, or up to 5 wt%, or up to 4.5 wt%, or up to 4 wt%, or up to 3.5 wt%, or up to 3 wt%, or up to 2.5 wt%, or up to 2 wt% of a polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier.

[0059] In another aspect, the composition further comprises about 0.1 wt% to about 15 wt% of a polycarbonate siloxane copolymer. In some aspects, the composition comprises at least 0.2 wt%, or at least 0.3 wt%, or at least 0.4 wt%, or at least 0.5 wt%, or at least 0.6 wt%, or at least 0.7 wt%, or at least 0.8 wt%, or at least 0.9 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or at least 2.5 wt%, or at least 3 wt%, or at least 3.5 wt%, or at least 4 wt%, or at least 4.5 wt%, or at least 5 wt%, or at least 6 wt%, or at least 7 wt%, or at least 8 wt%, or at least 9 wt%, or at least 10 wt%, or up to 15 wt%, or up to 14 wt%, or up to 13 wt%, or up to 12 wt%, or up to 11 wt%, or up to 10 wt%, or up to 9 wt%, or up to 8 wt%, or up to 7 wt%, or up to 6 wt%, or up to 5 wt% of polycarbonate-siloxane copolymer.

[0060] In some respects, the polycarbonate-siloxane copolymer has a siloxane content of about 15 wt% to about 45 wt%, based on the total weight of the polycarbonate-siloxane copolymer components. In other respects, the polycarbonate-siloxane copolymer has a siloxane content of about 15-25 wt% or about 18-22 wt% (e.g., opaque EXL with a siloxane content of about 20 wt%, available from SABIC) and / or about 35-45 wt% (e.g., a 40 wt% siloxane copolymer available from SABIC). In specific respects, the polycarbonate-siloxane copolymer has a siloxane content of about 35-40 wt%, or about 38-42 wt%, or about 40 wt%.

[0061] In specific respects, compositions according to various aspects of this disclosure do not include polycarbonate copolymers other than the polycarbonate-siloxane copolymers described herein. Other conventional polycarbonate copolymers—including, but not limited to, PC copolymers comprising (1) bisphenol A (PC) monomer units and isophthalic acid-resorcinol (ITR) ester units (e.g., SLX PC copolymers), and (2) high-flowability, ductile PC copolymers comprising sebacic acid monomer units and bisphenol A monomer units (e.g., HFD PC copolymers)—may prevent the compositions from having desired properties, such as, but not limited to, CTI grade PLC-0, packing thermal conductivity, and HDT properties.

[0062] Compositions according to various aspects of this disclosure may include at least one additional additive. This at least one additional additive may include, but is not limited to, acid scavengers, anti-dripping agents, antioxidants, antistatic agents, chain extenders, colorants, release agents, flow promoters, lubricants, plasticizers, quenchers, flame retardants, UV reflective additives, foaming agents, reinforcing agents, or combinations thereof.

[0063] In some aspects, the thermoplastic compositions described herein have a tensile elongation at break of at least 1.2% as determined according to ISO 527. In other aspects, the compositions have a tensile elongation at break of at least 1.3%, or at least 1.4%, or at least 1.5%, or at least 1.6%, or at least 1.7%, or at least 1.8%, or at least 1.9%, or at least 2%, or at least 2.1%, or at least 2.2%, or at least 2.3%, or at least 2.4% as determined according to ISO 527.

[0064] In some aspects, the composition has a tensile modulus of at least 6 gigapascals (GPa) as determined according to ISO 527. In other aspects, the composition has a tensile modulus of at least 6.5 GPa, or at least 7 GPa, or at least 7.5 GPa, or at least 8 GPa, or at least 8.5 GPa, or at least 9 GPa, or at least 9.5 GPa, or at least 10 GPa, or at least 10.5 GPa, or at least 11 GPa, or at least 11.5 GPa as determined according to ISO 527.

[0065] Compositions according to various aspects of this disclosure may have a strength of at least 20 KJ / m³ at 23°C, as determined according to ISO 180 / 1U. 2 The composition exhibits unnotched Izod impact strength (UNII). In other respects, the composition possesses at least 20.5 KJ / m² at 23°C, as determined according to ISO 180 / 1U. 2 or at least 21 KJ / m 2 or at least 21.5 KJ / m 2 or at least 22 KJ / m 2 or at least 22.5 KJ / m 2 or at least 23 KJ / m 2 or at least 23.5 KJ / m 2 or at least 24 KJ / m 2 or at least 24.5 KJ / m 2 or at least 25 KJ / m 2 or at least 25.5 KJ / m 2 or at least 26 KJ / m 2 or at least 26.5 KJ / m 2 UNII.

[0066] In some aspects, the composition has a packing thermal conductivity (TC) of at least 0.9 W / mK, or at least 1.0 W / mK, or at least 1.1 W / mK, or at least 1.2 W / mK, or at least 1.3 W / mK, or at least 1.4 W / mK, or at least 1.5 W / mK, or at least 1.6 W / mK, or at least 1.7 W / mK, or at least 1.8 W / mK, or at least 1.9 W / mK, or at least 2.0 W / mK. ISO 22007-2 describes the determination of thermal conductivity and thermal diffusivity using a transient planar heat source (heat plate). In principle, packing thermal conductivity or isotropic measurements are described according to this procedure. According to this disclosure, packing thermal conductivity is measured in watts per meter-Kelvin (W / mK) according to ISO 22007-2 and the following equation using anisotropic techniques:

[0067] TC accumulation = ,

[0068] Where TC_packed = packing thermal conductivity, TCtp = through-surface thermal conductivity (W / mK); and TCip = in-plane thermal conductivity (W / mK).

[0069] In another aspect, the composition has a heat distortion temperature (HDT) of at least 150°C, or at least 155°C, or at least 160°C, or at least 165°C, or at least 170°C, or at least 175°C, or at least 180°C, or at least 185°C, or at least 190°C, as determined according to ISO 75 / Af using a load of 1.8 MPa.

[0070] In another aspect, the composition has a Comparative Tracking Index (CTI) rating of PLC-0 as determined according to UL746A. In a particular aspect, the composition has a CTI rating of PLC-1 as determined according to UL746A, or in some aspects, a CTI rating of PLC-2 as determined according to UL746A. A PLC-0 rating means that the composition has a pass CTI rating at 300V, 400V, and 600V as determined according to UL746A. A PLC-1 rating means that the composition has a pass CTI rating at 300V and 400V as determined according to UL746A. A PLC-2 rating means that the composition has a pass CTI rating at 300V as determined according to UL746A.

[0071] Preparation method

[0072] One or any of the aforementioned components described herein can be first dry-blended with each other or with any combination of the aforementioned components, and then fed into the extruder from one or more feeders, or fed into the extruder individually from one or more feeders. Alternatively, the fillers used in this disclosure can be first treated into a masterbatch and then fed into the extruder. The components can be fed into the extruder from a throat hopper or any side feeder.

[0073] The extruder used in this disclosure may have a single screw, multiple screws, meshing screws rotating in the same or opposite directions, non-meshing screws rotating in the same or opposite directions, reciprocating screws, screws with pins, screws with sieves, barrels with pins, rollers, plungers, helical rotors, co-kneaders, disc processors, various other types of extrusion equipment, or combinations including at least one of the aforementioned extruders.

[0074] The components may also be mixed together and then melt-blended to form a thermoplastic composition. Melt blending of the components involves the use of shear force, tensile force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy, or a combination of at least one of the foregoing forms of force or energy.

[0075] If the resin is a semi-crystalline organic polymer, the barrel temperature on the extruder during compounding can be set to a temperature at which at least a portion of the polymer has reached approximately greater than or equal to the melt temperature; or if the resin is an amorphous resin, the barrel temperature can be set to a temperature at which at least a portion of the polymer has reached approximately greater than or equal to the flow point (e.g., glass transition temperature).

[0076] If desired, the mixture comprising the foregoing components can undergo multiple blending and forming steps. For example, the thermoplastic composition can first be extruded and formed into granules. The granules can then be fed into a molding machine, where they can be formed into any desired shape or product. Alternatively, the thermoplastic composition produced in a single melt mixer can be formed into sheets or bundles and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0077] In some aspects, the melt temperature during the process of this invention can be kept as low as possible to avoid excessive thermal degradation of the components. In some aspects, the melt temperature is maintained between about 230°C and about 350°C, but higher temperatures can be used provided that the residence time of the resin in the processing equipment remains relatively short. In some aspects, the melt-treated composition exits the processing equipment, such as an extruder, through a small outlet orifice in a die. The resulting bundle of molten resin can be cooled by passing the bundle through a water bath. The cooled bundle can be cut into pellets for packaging and further processing.

[0078] Products

[0079] In some aspects, this disclosure relates to molded articles, formed articles, or molded articles comprising thermoplastic compositions. Thermoplastic compositions can be molded into useful molded articles in a variety of ways, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming, to form articles and structural components, for example, personal or commercial electronic devices, including but not limited to cellular phones, tablet computers, personal computers, laptop computers, and portable computers, as well as other such devices, medical applications, RFID applications, automotive applications, etc. In another aspect, the article is extruded. In yet another aspect, the article is injection molded.

[0080] Specifically, the products are radar components or high-voltage components.

[0081] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from supplementary claims attached to the same independent claim.

[0082] All aspects of this disclosure

[0083] In all respects, this disclosure relates to and includes at least the following aspects.

[0084] Aspect 1. A thermoplastic composition comprising, consisting of, or substantially consisting of:

[0085] a. Approximately 10 wt% to approximately 40 wt% of PBT (polybutylene terephthalate) component;

[0086] b. Approximately 5 wt% to less than 10 wt% of glass fiber components;

[0087] c. About 50 wt% to about 70 wt% of a mineral filler component, said mineral filler component comprising aluminum silicate, alumina, magnesium oxide or a combination thereof;

[0088] d. About 0.1 wt% to about 10 wt% of an impact modifier component, said impact modifier component comprising about 0.4 wt% to about 3.5 wt% of ethylene-ethyl acrylate copolymer (EEA) and about 0.5 wt% to about 3 wt% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA); and

[0089] e. Optional polycarbonate-siloxane copolymer component

[0090] The combined weight percentage of all components does not exceed 100 wt%, and all weight percentage values ​​are based on the total weight of the composition.

[0091] The composition therein does not contain any polycarbonate copolymer other than the optional polycarbonate-siloxane copolymer in element (e), and

[0092] The composition contains a Comparative Tracking Index (CTI) rating of PLC-0 as determined according to UL746A.

[0093] Aspect 2. The thermoplastic composition according to Aspect 1, wherein the PBT component comprises high-flow PBT with an intrinsic viscosity of less than 1.0 dL / g and low-flow PBT with an intrinsic viscosity of at least 1.0 dL / g, wherein the intrinsic viscosity is measured according to ASTM D2857 in a 60:40 phenol / tetrachloroethane mixture.

[0094] Aspect 3. The thermoplastic composition according to aspect 2, wherein the composition comprises the high-flow PBT and the low-flow PBT in a ratio of 2:1 to 1:2.

[0095] Aspect 4. The thermoplastic composition according to any one of Aspects 1 to 3, wherein the impact modifier component further comprises 0.1 wt% to about 9 wt% of a polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier.

[0096] Aspect 5. The thermoplastic composition according to any one of Aspects 1 to 4, wherein the composition further comprises about 0.1 wt% to about 15 wt% of a polycarbonate siloxane copolymer.

[0097] Aspect 6. The thermoplastic composition according to aspect 5, wherein the polycarbonate siloxane copolymer has a siloxane content of about 15 wt% to about 45 wt%.

[0098] Aspect 7. The thermoplastic composition according to any one of Aspects 1 to 6, wherein the glass fiber component comprises circular glass fibers.

[0099] Aspect 8. The thermoplastic composition according to any one of Aspects 1 to 7, wherein the composition comprises at least one additional additive.

[0100] Aspect 9. The thermoplastic composition according to aspect 8, wherein the at least one additional additive comprises an acid scavenger, an anti-dripping agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a release agent, a flow promoter, a lubricant, a plasticizer, a quencher, a flame retardant, a UV reflective additive, a foaming agent, a reinforcing agent, or a combination thereof.

[0101] Aspect 10. The thermoplastic composition according to any one of aspects 1 to 9, wherein the composition comprises at least 1.2% elongation at break as determined according to ISO 527.

[0102] Aspect 11. The thermoplastic composition according to any one of Aspects 1 to 10, wherein the composition comprises a tensile modulus of at least 6 gigapascals (GPa) as determined according to ISO 527.

[0103] Aspect 12. The thermoplastic composition according to any one of Aspects 1 to 11, wherein the composition comprises at least 20 KJ / m² at 23°C as determined according to ISO 180 / 1U. 2 Unnotched Izod impact strength (UNII).

[0104] Aspect 13. The thermoplastic composition according to any one of Aspects 1 to 12, wherein the composition comprises a thermal conductivity (TC) of at least 0.9 W / mK as measured in watts per meter-Kelvin (W / mK) according to anisotropic techniques as per ISO 22007-2.

[0105] Aspect 14. The thermoplastic composition according to any one of Aspects 1 to 13, wherein the composition comprises a heat deflection temperature (HDT) of at least 150°C as determined according to ISO 75 / Af using a load of 1.8 MPa.

[0106] Aspect 15. The thermoplastic composition according to any one of Aspects 1 to 14, wherein the composition comprises a comparative tracking index (CTI) rating of PLC-0 or PLC-1 and / or PLC-2 as determined according to UL746A.

[0107] Aspect 16. An article comprising the thermoplastic composition according to any one of aspects 1 to 15.

[0108] Aspect 17. The article of manufacture according to aspect 16, wherein the article of manufacture is a radar assembly or a high-voltage assembly.

[0109] Example

[0110] The following examples are provided to provide a complete disclosure and description to those skilled in the art on how to manufacture and evaluate the compounds, compositions, articles, apparatus, and / or methods claimed herein, and are intended to be illustrative only and not to limit this disclosure. Efforts have been made to ensure accuracy regarding figures (e.g., amounts, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperatures are in °C or at ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise stated, percentages of compositions refer to wt%.

[0111] There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperature, pressure) and other reaction ranges and conditions that can be used to optimize the purity and yield of the product obtained by the described process. Optimizing such process conditions requires only reasonable and routine experiments.

[0112] The components used in one or more compositions described herein are listed in Table 1:

[0113] Table 1 - Components

[0114]

[0115]

[0116] The composition is prepared by mixing the components, extruding them into granules, and molding them into samples for testing. Table 2 lists typical extrusion conditions:

[0117] Table 2 – Extrusion Conditions

[0118]

[0119] Table 3 lists typical molding conditions:

[0120] Table 3 - Molding Conditions

[0121]

[0122] Prepare aluminum silicate-based compositions according to Table 4A:

[0123] Table 4A – PBT compositions containing thermally conductive aluminosilicate filler

[0124]

[0125] Prepare alumina-based compositions according to Table 4B:

[0126] Table 4B – PBT compositions containing thermally conductive alumina filler

[0127]

[0128] Tables 5A and 5B list the properties of the compositions in Tables 4A and 4B, respectively:

[0129] Properties of compositions (aluminum silicate) in Tables 5A-4A

[0130]

[0131] Properties of compositions (alumina) in Tables 5B – 4B

[0132]

[0133] Tensile strength, elongation at break, and tensile modulus are evaluated according to ISO 527. Unnotched Izod impact strength (UNII) at 23°C is evaluated according to ISO 180 / 1U. Heat deflection temperature (HDT) is evaluated under a 1.8 MPa load according to ISO 75 / Af. Comparative tracking index (CTI) at a specified voltage is evaluated according to UL 746A. A "pass" rating is given when the average number of drops at a specific voltage is 100. A "fail" rating is given when the average number of drops is less than 100.

[0134] The packing thermal conductivity is measured in watts per meter-Kelvin (W / mK) according to ISO 22007-2 and the following equation based on anisotropic techniques:

[0135] TC accumulation = ,

[0136] Where TC_packed = packing thermal conductivity, TCtp = through-surface thermal conductivity (W / mK); and TCip = in-plane thermal conductivity (W / mK).

[0137] Articles made from compositions according to aspects of this disclosure have one or more of the following properties: tensile strength of at least 50 MPa; elongation at break of at least 1.2%; tensile modulus of at least 6 GPa; and UNII of at least 20 KJ / m. 2 The stacked TC is at least 0.9 W / mK; the HDT is at least 150°C; and it meets the CTI rating at 300 V, 400 V, and / or 600 V as determined by UL746A. Such products are suitable for applications such as, but not limited to, high-voltage connectors and radar back covers.

[0138] The compositions in Tables 4A and 4B, which include EMAGMA and EEA impact modifiers, are expected to have CTI pass ratings at 300 V, 400 V, and / or 600 V as determined according to UL 746A. Additionally, compositions including polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier (Hytrel®) are expected to have improved melt flow properties. Adding reinforcing fibers (glass fibers) improves the HDT properties of the compositions, but without a suitable impact modifier component, the compositions will not meet the expected CTI pass rating at 600 V. Adding excessive impact modifiers (such as EEA) results in a decrease in mechanical properties. While the best overall performance has been observed in compositions including ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA), and polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier (Hytrel®), compositions including only EEA and EMAGMA have properties suitable for many applications.

[0139] Comparative compositions including other polycarbonate copolymers and / or another type of PBT (IQ PBT) were prepared and tested, as shown in Tables 6 and 7:

[0140] Table 6 – Comparative Compositions

[0141]

[0142] Compare the properties of the compositions:

[0143] Properties of the compositions (Tables 7-6)

[0144]

[0145] Comparative compositions, including those with other PC copolymers, did not meet the desired packing TC (at least 0.9 W / mK) and HDT (at least 150°C) requirements. Furthermore, only composition C4 exhibited the pass CTI rating (i.e., PLC-0 rating) at 300 V, 400 V, and 600 V as determined according to UL746A.

[0146] The above description is intended to be illustrative and not restrictive. For example, the examples (or one or more aspects thereof) described above may be used in combination with each other. Other aspects may be used, as would be done by one of ordinary skill in the art upon review of the above description. An abstract is provided to conform to 37 CFR §1.72(B), thereby allowing the reader to quickly determine the nature of the technical disclosure. It is submitted on the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Moreover, in the above detailed description, various features may be grouped together to simplify this disclosure. This should not be construed as meaning that features of the disclosure not claimed are necessary for any claim. Rather, the subject matter of the invention may lie in fewer features than all of a particular aspect of the disclosure. Therefore, the following claims are hereby incorporated, as examples or aspects, wherein each claim exists as a separate aspect, and it is contemplated herein that such aspects may be combined with each other in various combinations or arrangements. The scope of this disclosure should be determined by reference to the appended claims and the full scope of the equivalent forms granted by such claims.

Claims

1. A thermoplastic composition comprising: a. Approximately 10 wt% to approximately 40 wt% of PBT (polybutylene terephthalate) component; b. Approximately 5 wt% to less than 10 wt% of glass fiber components; c. About 50 wt% to about 70 wt% of a mineral filler component, said mineral filler component comprising aluminum silicate, alumina, magnesium oxide or a combination thereof; d. About 0.1 wt% to about 10 wt% of an impact modifier component, said impact modifier component comprising about 0.4 wt% to about 3.5 wt% of ethylene-ethyl acrylate copolymer (EEA) and about 0.5 wt% to about 3 wt% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMAGMA); and e. Optional polycarbonate-siloxane copolymer component The combined weight percentage of all components does not exceed 100 wt%, and all weight percentage values ​​are based on the total weight of the composition. The composition therein does not contain any polycarbonate copolymer other than the optional polycarbonate-siloxane copolymer in element (e), and The composition contains a Comparative Tracking Index (CTI) rating of PLC-0 as determined according to UL746A.

2. The thermoplastic composition of claim 1, wherein the PBT component comprises high-flow PBT with an intrinsic viscosity of less than 1.0 dL / g and low-flow PBT with an intrinsic viscosity of at least 1.0 dL / g, wherein the intrinsic viscosity is measured according to ASTM D2857 in a 60:40 phenol / tetrachloroethane mixture.

3. The thermoplastic composition of claim 2, wherein the composition comprises the high-flow PBT and the low-flow PBT in a ratio of 2:1 to 1:

2.

4. The thermoplastic composition according to any one of claims 1 to 3, wherein the impact modifier component further comprises 0.1 wt% to about 9 wt% of a polybutylene terephthalate / butylene isophthalate-co-polyoxybutylene impact modifier.

5. The thermoplastic composition according to any one of claims 1 to 4, wherein the composition further comprises about 0.1 wt% to about 15 wt% of a polycarbonate siloxane copolymer, wherein the polycarbonate siloxane copolymer has a siloxane content of about 15 wt% to about 45 wt%.

6. The thermoplastic composition according to any one of claims 1 to 5, wherein the composition comprises at least one additional additive.

7. The thermoplastic composition according to claim 6, wherein the at least one additional additive comprises an acid scavenger, an anti-dripping agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a release agent, a flow promoter, a lubricant, a plasticizer, a quencher, a flame retardant, a UV reflective additive, a foaming agent, a reinforcing agent, or a combination thereof.

8. The thermoplastic composition according to any one of claims 1 to 7, wherein the composition comprises at least 1.2% elongation at break as determined according to ISO 527.

9. The thermoplastic composition according to any one of claims 1 to 8, wherein the composition comprises a tensile modulus of at least 6 gigapascals (GPa) as determined according to ISO 527.

10. The thermoplastic composition of any one of claims 1 to 9, wherein the composition comprises an unnotched Izod impact strength (UNII) of at least 20 KJ / m2 at 23 °C as determined according to ISO 180 / 1 U. 2 10. The thermoplastic composition of any one of claims 1 to 9, wherein the composition comprises an unnotched Izod impact strength (UNII) of at least 20 KJ / m2 at 23 °C as determined according to ISO 180 / 1 U.

11. The thermoplastic composition according to any one of claims 1 to 10, wherein the composition comprises a thermal conductivity (TC) of at least 0.9 W / mK as measured in watts per meter-Kelvin (W / mK) according to anisotropic techniques as per ISO 22007-2.

12. The thermoplastic composition according to any one of claims 1 to 11, wherein the composition comprises a heat deflection temperature (HDT) of at least 150°C as determined according to ISO 75 / Af using a load of 1.8 MPa.

13. The thermoplastic composition according to any one of claims 1 to 12, wherein the composition comprises a comparative tracking index (CTI) rating of PLC-0 or PLC-1 and / or PLC-2 as determined according to UL746A.

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

15. The article of claim 14, wherein the article of claim 14 is a radar assembly or a high-voltage assembly.

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