Flame retardant polycarbonate compositions having good tracking index, modulus and impact properties

Abstract

A thermoplastic composition includes: about 35 wt% to about 65 wt% of a polycarbonate (PC) homopolymer component; 0 wt% to about 50 wt% of a polybutylene terephthalate (PBT) component; about 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and about 0.1 wt% to about 20 wt% of an aromatic bromine and cyanurate flame retardant component. The total siloxane content of the composition is no greater than 2.0 wt%. In some aspects, the composition has good comparative tracking index (CTI) performance in addition to good mechanical properties, such as high modulus and impact resistance.

Description

Technical Field

[0001] This disclosure relates to polycarbonate compositions, particularly polycarbonate compositions having improved comparative tracking index and mechanical properties. Background Technology

[0002] The Comparative Tracking Index (CTI) measures the maximum voltage (in volts) a material can withstand without developing tracking after 50 drops of contaminated water. Tracking is defined as the formation of a conductive path due to electrical stress, humidity, and contamination. Insulating materials should have a high Comparative Tracking Index, defined as a CTI of 600V as measured by IEC 60112 or a CTI of PLC0 as measured by ASTM D3638. Thermoplastic polymers, including blends of polycarbonate (PC) and polybutylene terephthalate (PBT), are used as insulation materials in connectors for solar photovoltaic (PV), electric vehicle (EV), and other electrical equipment. However, developing PC / PBT blends that possess both high CTI and high modulus and impact resistance is very challenging. Many high-performance end products require high modulus and impact resistance.

[0003] In some applications, flame-retardant PC / PBT blends include brominated flame retardants, such as tetrabromobisphenol A-based flame retardants (CAS 79-94-7), including brominated polycarbonates or other brominated aromatic oligomers. These blends may also include impact modifiers to improve modulus and impact resistance. However, such conventional compositions cannot achieve high CTI performance.

[0004] The aspects of this disclosure address these and other shortcomings. Summary of the Invention

[0005] Various aspects of this disclosure relate to thermoplastic compositions comprising: about 35 wt% to about 65 wt% of a polycarbonate (PC) homopolymer component; 0 wt% to about 50 wt% of a polybutylene terephthalate (PBT) component; about 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and about 0.1 wt% to about 20 wt% of an aromatic bromide and cyanurate flame retardant component. The total siloxane content of the composition is not greater than 2.0 wt%. In some aspects, in addition to good mechanical properties, such as high modulus and impact resistance, the composition also exhibits good comparative tracking index (CTI) performance. Detailed Implementation

[0006] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it should be understood that, unless otherwise specified, they are not limited to specific synthetic methods, or, unless otherwise specified, to specific reagents, as they can certainly vary. 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 dependent claims that are subordinate 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 particular order. Therefore, in no way is an order intended to be inferred unless the method claims do not actually describe the order in which the steps are followed, or unless the claims or description specifically state that the steps are limited to a particular order. This applies to any possible uninterpreted basis, including: logical matters concerning the arrangement of steps or procedures; literal meanings derived from grammatical structure or punctuation; and 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 associated with the listed publications.

[0010] The thermoplastic composition according to this disclosure comprises: about 35 wt% to about 65 wt% of a polycarbonate (PC) homopolymer component; 0 wt% to about 50 wt% of a polybutylene terephthalate (PBT) component; about 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and about 0.1 wt% to about 20 wt% of an aromatic bromide and cyanurate flame retardant component. The total siloxane content of the composition is not greater than 2.0 wt%. In some aspects, the composition has good relative tracking index, high modulus, and good impact resistance. These properties are balanced by selecting the type and / or amount of flame retardant and impact modifier. In particular, combining a flame retardant comprising aromatic bromide and cyanurate with an acrylic core-shell impact modifier can provide a composition with the desired properties.

[0011] definition

[0012] It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be restrictive. 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.

[0013] As used in the specification and appended claims, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include plural indicators. Thus, for example, reference to “polycarbonate copolymer component” includes a mixture of two or more polycarbonate copolymers.

[0014] As used in this article, the term "combination" includes blends, mixtures, alloys, reaction products, etc.

[0015] 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 valid both in relation 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, then “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, then 11, 12, 13, and 14 are also disclosed.

[0016] As used herein, the terms “about” and “at or about” mean that the quantity or value in question may be a specified value, approximately a specified value, or approximately the same as a specified 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.

[0017] 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 contemplated 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 each combination and arrangement and possible modifications of the compound are 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 to be disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups AE, BF, and CE are considered to be disclosed. This concept applies to all aspects of this application, including but not limited to 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.

[0018] References to the weight parts of a specific element or component in the composition or article in the specification and the concluding claims indicate the weight relationship between the element or component and any other element or component in the composition or article, 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.

[0019] 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.

[0020] 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:"

[0021]

[0022] Where M i It is the molecular weight of the chain, and N i This 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 .

[0023] 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:

[0024]

[0025] 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 well known to those skilled in the art. w .

[0026] As used herein, the terms “polydispersity index” or “PDI” are used interchangeably and are defined by the following formula:

[0027]

[0028] 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.

[0029] As used herein, the interchangeable terms “BisA,” “BPA,” or “bisphenol A” refer to compounds having a structure represented by the following formula:

[0030]

[0031] 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.

[0032] As used herein, “polycarbonate” means 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.

[0033] The terms “residue” and “structural unit” used to describe the composition of the polymer are synonymous throughout the specification.

[0034] 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 compositions or formulations equals 100.

[0035] Unless otherwise stated herein, all testing standards are current and up-to-date at the time of filing of this application.

[0036] Each raw material used in the example and / or comparative compositions described herein is commercially available and / or its production method is known to those skilled in the art.

[0037] 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.

[0038] thermoplastic composition

[0039] The thermoplastic compositions according to various aspects of this disclosure comprise: about 35 wt% to about 65 wt% of a polycarbonate (PC) homopolymer component; 0 wt% to about 50 wt% of a polybutylene terephthalate (PBT) component; about 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and about 0.1 wt% to about 20 wt% of an aromatic bromide and cyanurate flame retardant component. The total siloxane content of the composition is not greater than 2.0 wt%. 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.

[0040] In some aspects, the polycarbonate homopolymer component may include a bisphenol A (BPA) homopolymer. Suitable polycarbonate homopolymers are available from SABIC. In some aspects, the composition comprises about 35 wt% to about 65 wt% of a polycarbonate homopolymer component. In other aspects, the composition comprises at least 35 wt%, at least 37 wt%, at least 39 wt%, at least 41 wt%, at least 43 wt%, at least 45 wt%, at least 47 wt%, at least 49 wt%, at least 51 wt%, at least 53 wt%, up to 65 wt%, up to 63 wt%, up to 61 wt%, up to 59 wt%, up to 57 wt%, up to 55 wt%, up to 53 wt%, up to 51 wt%, up to 49 wt%, up to 47 wt%, or up to 45 wt% of a polycarbonate homopolymer component.

[0041] As used herein, “polybutylene terephthalate” (PBT) can be used interchangeably with poly(1,4-butylene terephthalate). Polybutylene terephthalate is a polyester. Polyesters, including poly(alkylene dicarboxylate), liquid crystal polyesters, and polyester copolymers, can be used in the thermoplastic compositions of this disclosure. In some aspects, the composition comprises 0 wt% to about 50 wt% of a polybutylene terephthalate component. In other respects, the composition comprises greater than 0 wt%, at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 9 wt%, at least 11 wt%, at least 13 wt%, at least 15 wt%, at least 17 wt%, at least 19 wt%, at least 21 wt%, at least 23 wt%, up to 50 wt%, up to 48 wt%, up to 45 wt%, up to 42 wt%, up to 40 wt%, up to 38 wt%, up to 35 wt%, up to 32 wt%, up to 30 wt%, up to 28 wt%, up to 26 wt%, up to 24 wt%, up to 22 wt%, up to 20 wt%, up to 18 wt%, up to 16 wt%, or 10 wt% to 50 wt% of a polybutylene terephthalate component.

[0042] The thermoplastic composition comprises about 5 wt% to about 20 wt% of a core-shell acrylic polymer component, which can act as an impact modifier. In some aspects, the composition comprises at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, at least 15 wt%, up to 20 wt%, up to 19 wt%, up to 18 wt%, up to 17 wt%, up to 16 wt%, up to 15 wt%, up to 14 wt%, up to 13 wt%, up to 12 wt%, up to 11 wt%, up to 10 wt%, 10 wt% to 15 wt%, or 5 wt% to 15 wt% of a core-shell acrylic polymer component.

[0043] Some aspects of the core-shell acrylic polymer component include siloxanes. Exemplary core-shell acrylic polymers including siloxanes are available from Mitsubishi Chemical, including but not limited to S-2501 (about 10 wt% siloxane), S-2200 (about 8 wt% siloxane), and S-2030 (about 30 wt% siloxane).

[0044] In other respects, core-shell acrylic polymers do not include siloxanes. Examples include, but are not limited to, core-shell acrylic polymers based on 2-acrylic acid and butyl acrylate-methyl methacrylate (CAS numbers 31261-08-2 and 25852-37-3, purchased from Dow), and core-shell acrylic polymers based on butyl acrylate-methyl methacrylate (CAS number 25852-37-3, purchased from Dow).

[0045] The total siloxane content of the composition is not greater than 2.0 wt%. In other respects, the composition has a total siloxane content of up to 1.9 wt%, up to 1.8 wt%, up to 1.7 wt%, up to 1.6 wt%, up to 1.5 wt%, up to 1.4 wt%, up to 1.3 wt%, up to 1.2 wt%, up to 1.1 wt%, up to 1.0 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 0.6 wt%, at least 0.7 wt%, at least 0.8 wt%, or at least 0.9 wt%.

[0046] The thermoplastic composition comprises about 0.1 wt% to about 20 wt% of an aromatic brominated and cyanurate flame retardant component. An exemplary aromatic brominated and cyanurate flame retardant component is FR-245, purchased from ICL, which is tris(tribromophenyl) cyanurate (CAS: 25713-60-4) with a bromine content of about 67 wt%. In some aspects, the composition comprises at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 0.7 wt%, at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, up to 20 wt%, up to 19 wt%, up to 18 wt%, up to 17 wt%, up to 16 wt%, up to 15 wt%, up to 14 wt%, up to 13 wt%, up to 12 wt%, up to 11 wt%, or up to 10 wt% of an aromatic brominated and cyanurate flame retardant component. As shown in the examples, it has been found that PC / PBT compositions comprising aromatic brominated and cyanurate flame retardants have improved properties, such as CTI and mechanical properties, compared to compositions comprising other flame retardants, including brominated flame retardants such as brominated PC.

[0047] In some aspects, the composition further comprises a flame retardant synergist, which may help to further improve the FR performance of the composition. An exemplary FR synergist is Sb2O3 / PBT (80 / 20 wt%), available from SABIC. In a particular aspect, the composition comprises about 0.5 wt% to about 8 wt% of the FR synergist. In other aspects, the composition comprises at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3.0 wt%, at least 3.5 wt%, at least 4.0 wt%, up to 8 wt%, up to 7.5 wt%, up to 7.0 wt%, up to 6.5 wt%, up to 6.0 wt%, up to 5.5 wt%, up to 5.0 wt%, or up to 4.5 wt% of the FR synergist.

[0048] In some aspects, the composition further comprises greater than 0 wt% to about 15 wt% of a polycarbonate copolymer component. In a particular aspect, the composition comprises at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, up to 15 wt%, up to 14 wt%, up to 13 wt%, up to 12 wt%, or up to 11 wt% of a polycarbonate copolymer component.

[0049] In some respects, the polycarbonate copolymer component may include isophthalate-terephthalate-resorcinol monomer units and bisphenol A monomer units, sebacic acid monomer units and bisphenol A monomer units, polycarbonate-siloxane copolymers, or combinations thereof.

[0050] In some aspects, the polycarbonate copolymer component may include a copolyester carbonate. The copolyester carbonate copolymer may include ester units of the following formula.

[0051]

[0052] Where D is a divalent group derived from a dihydroxy compound, and can be, for example, C. 2-30 Alkylene, C 3-30 Alicyclic groups, C 6-30 An aromatic group or a polyoxyalkylene group, wherein the alkylene group contains 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and a T divalent group derived from a dicarboxylic acid, and may be, for example, C. 2-30 Alkylene, C 6-30 Alicyclic groups, C 6-30 alkyl aromatic groups or C 6-30 Aromatic groups.

[0053] Examples of aromatic dicarboxylic acids from which the T group in the ester originates include isophthalic acid or terephthalic acid, 1,2-bis(p-carboxyphenyl)ethane, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dibenzoic acid, and combinations including at least one of the above acids. Acids containing fused rings, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acid, may also be present. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, or combinations thereof. Specific dicarboxylic acids include combinations of isophthalic acid and terephthalic acid, wherein the weight ratio of isophthalic acid to terephthalic acid is 99:1 to 1:99. On the one hand, D is C. 2-6 Alkylene, and T is a phenylene, m-phenylene, naphthalene, divalent alicyclic group or a combination thereof. This type of polyester includes poly(alkylene terephthalate).

[0054] On the one hand, the ester unit of the polyester or polyester block includes an aryl ester unit, said aryl ester unit being derived from the reaction product of an equivalent of an isophthalic acid derivative and / or a terephthalic acid derivative with resorcinol of the following formula.

[0055]

[0056] Each R f Independently for C 1-12 Alkyl or halogen, and u is 0 to 4. It should be understood that when u is 0, R... f It is hydrogen. Typically, the halogen can be chlorine or bromine. On one hand, the -OH groups are meta-substituted with each other, and R... f Compounds like u described above are also commonly referred to herein as resorcinol. Examples of compounds that can be represented by this formula include resorcinol (where u is 0), substituted resorcinol compounds such as 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-tert-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromoresorcinol, etc.; catechol; hydroquinone; substituted p-phenylene... Diphenols such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetratert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc.; or combinations including at least one of the above compounds.

[0057] Such aryl ester units are also referred to herein as isophthalate-terephthalate-resorcinol ester units, and sometimes simply as ITR ester units. As used herein, the isophthalate-terephthalate-resorcinol ester unit comprises a combination of isophthalate, terephthalate, and resorcinol ester. In one particular aspect, the isophthalate-terephthalate-resorcinol ester unit comprises a combination of isophthalate-resorcinol ester units and terephthalate-resorcinol ester units. In one particular aspect, when u is 0, the aryl ester unit comprises the isophthalate-terephthalate-resorcinol ester unit, wherein the resorcinol is 1,3-dihydroxybenzene. Exemplary aromatic polyester blocks include poly(isophthalate-terephthalate-resorcinol) ester, poly(isophthalate-terephthalate-bisphenol A) ester, poly[(isophthalate-terephthalate-resorcinol) ester-co-(isophthalate-terephthalate-bisphenol A)] ester, or combinations including at least one of these. In one aspect, a useful aryl ester polyester block is poly(isophthalate-terephthalate-resorcinol) ester. In a particular aspect, the copolyester carbonate copolymer includes an ITR block and a polycarbonate block, as shown in the following formula:

[0058]

[0059] Where x is the mol% of the ITR ester block and y is the mol% of the polycarbonate block. An exemplary copolyester carbonate copolymer is SLX 20 / 80 resin purchased from SABIC. SLX 20 / 80 comprises 20 mol% of ITR block and 80 mol% of PC block.

[0060] In other respects, the molar ratio of the ITR ester units to the polycarbonate monomer units of the copolyester carbonate copolymer is about 15:85 to about 95:5, or about 20:80 to about 90:10, or about 15:85 to about 25:75, or about 18:82 to about 22:78, or about 20:80, or about 85:15 to about 95:5, or about 88:12 to about 92:8, or about 90:10.

[0061] In some aspects, the polycarbonate copolymer component includes a polycarbonate-siloxane copolymer, wherein the siloxane content of the polycarbonate-siloxane copolymer is from about 5 wt% to about 45 wt% based on the total weight of the polycarbonate-siloxane copolymer component. In other aspects, the siloxane content of the polycarbonate-siloxane copolymer is about 4-8 wt% (e.g., a transparent EXL purchased from SABIC with a siloxane content of about 6 wt%), about 18-22 wt% (e.g., an opaque EXL purchased from SABIC with a siloxane content of about 20 wt%), and / or about 35-45 wt% (e.g., a 40 wt% siloxane copolymer purchased from SABIC).

[0062] In one particular aspect, the composition comprises a PC copolymer, such as a sebacic acid / BPA PC copolymer comprising sebacic acid monomer units and bisphenol A monomer units. Sebacic acid has the following structure:

[0063]

[0064] Bisphenol A has the following structure:

[0065]

[0066] As copolymers, sebacic acid monomers impart good flowability and ductility to the copolymers at lower processing temperatures, while BPA monomers provide improved thermal and modulus properties. Exemplary sebacic acid / BPA copolymers comprise high molecular weight (Mw) high flowability / ductility (HFD) polycarbonates, low Mw HFD polycarbonates, or combinations thereof. In some aspects, the composition comprises a polycarbonate copolymer component comprising about 0.1 mol% to about 10 mol% of sebacic acid monomer units and about 90 mol% to about 99.9 mol% of bisphenol A monomer units.

[0067] In some aspects, the composition includes at least one additional additive. This additional additive may include, but is not limited to, deacidifying agents, anti-drip agents, antioxidants, antistatic agents, chain extenders, colorants, release agents, flow promoters, lubricants, plasticizers, quenchers, flame retardants, UV reflective additives, impact modifiers, foaming agents, reinforcing agents, or combinations thereof.

[0068] In some aspects, the composition comprises at least one additional additive in amounts of about 0.1 wt% to about 8 wt%. In other aspects, the composition comprises at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 0.7 wt%, at least 0.9 wt%, at least 1.1 wt%, at least 1.3 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, up to 8 wt%, up to 7.5 wt%, up to 7.0 wt%, up to 6.5 wt%, up to 6.0 wt%, up to 5.5 wt%, up to 5.0 wt%, up to 4.5 wt%, up to 4.0 wt%, up to 3.5 wt%, or up to 3.0 wt%.

[0069] In certain aspects, at least one additional additive includes an anti-drip agent, such as, but not limited to, polytetrafluoroethylene (PTFE). An example PTFE anti-drip agent is PTFE encapsulated with a styrene-acrylonitrile copolymer, commonly referred to as TSAN. In certain aspects, the composition comprises 0.1 wt% to 2 wt% TSAN. In other respects, the composition comprises at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 0.6 wt%, at least 0.7 wt%, at least 0.8 wt%, up to 2 wt%, up to 1.9 wt%, up to 1.8 wt%, up to 1.7 wt%, up to 1.6 wt%, up to 1.5 wt%, up to 1.4 wt%, up to 1.3 wt%, up to 1.2 wt%, up to 1.1 wt%, up to 1 wt%, up to 0.9 wt%, up to 0.8 wt%, up to 0.7 wt%, up to 0.6 wt%, up to 0.5 wt%, up to 0.4 wt%, up to 0.3 wt%, up to 0.2 wt%, or up to 0.1 wt% of TSAN.

[0070] The compositions according to various aspects of this disclosure may have improved performance compared to conventional compositions, particularly those that do not include aromatic bromides and cyanurate flame retardant components. In some aspects, the comparative tracking index (CTI) of the composition is measured as CTI 600V according to IEC 60112, or as CTI PLC0 according to ASTM D3638.

[0071] In some respects, the flexural modulus of the composition is at least 1.9 gigapascals (GPa) as measured according to ASTM D790 at a speed of 1.27 mm / min. In other respects, the flexural modulus of the composition is at least 1.95 GPa, at least 2.0 GPa, at least 2.05 GPa, at least 2.1 GPa, or at least 2.15 GPa as measured according to ASTM D790 at a speed of 1.27 mm / min.

[0072] In certain aspects, the composition has a notched Izod impact strength of at least 650 J / m at 25°C, as determined by ASTM D256. In other aspects, the composition has a notched Izod impact strength of at least 675 J / m, at least 700 J / m, at least 725 J / m, at least 750 J / m, at least 775 J / m, at least 800 J / m, at least 825 J / m, or at least 850 J / m, as determined by ASTM D256.

[0073] In other respects, the composition has a V0 flame retardant rating, as tested by UL94 at a thickness of 1.0 mm.

[0074] In certain aspects, the composition has a p(FTP) flame retardancy of at least 0.9, as tested according to UL94 at a thickness of 1.0 mm. In some aspects, the composition has a p(FTP) flame retardancy of at least 0.91, at least 0.92, at least 0.93, at least 0.94, at least 0.95, at least 0.96, at least 0.97, at least 0.98, or at least 0.99, as tested according to UL94 at a thickness of 1.0 mm.

[0075] Manufacturing method

[0076] 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.

[0077] 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-pack processors, various other types of extrusion equipment, or combinations including at least one of the aforementioned extruders.

[0078] 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.

[0079] 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 a temperature greater than or equal to approximately 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 a temperature greater than or equal to approximately the flow point (e.g., glass transition temperature).

[0080] If desired, the mixture comprising the aforementioned components can undergo multiple blending and molding steps. For example, the thermoplastic composition can first be extruded and molded into granules. The granules can then be fed into a molding machine, where they can be molded into any desired shape or product. Alternatively, the thermoplastic composition produced in a single melt mixer can be molded into sheets or bundles and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0081] 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 shredded into pellets for packaging and further processing.

[0082] Products

[0083] In some aspects, this disclosure relates to molded articles, shaped 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, such as 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. In some aspects, the article is an electrical connector, an insulating housing, insulating material for solar photovoltaic or electric vehicles, or another electrical equipment component.

[0084] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from dependent claims that are subordinate to the same independent claim.

[0085] All aspects of this disclosure

[0086] In all respects, this disclosure relates to and includes at least the following aspects.

[0087] Aspect 1. A thermoplastic composition comprising, consisting of, or substantially consisting of:

[0088] The polycarbonate (PC) homopolymer component comprises approximately 35 wt% to approximately 65 wt%.

[0089] 0 wt% to approximately 50 wt% of polybutylene terephthalate (PBT) component;

[0090] About 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and

[0091] Aromatic brominated and cyanurate flame retardant components, from about 0.1 wt% to about 20 wt%.

[0092] The total siloxane content of the composition is not greater than 2.0 wt%, and

[0093] 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.

[0094] Aspect 2. The thermoplastic composition according to aspect 1, wherein the flame retardant component comprises tris(tribromophenyl)cyanurate.

[0095] Aspect 3. The thermoplastic composition according to aspect 1 or 2, wherein the composition further comprises more than 0 wt% to about 15 wt% of a polycarbonate copolymer component.

[0096] Aspect 4. The thermoplastic composition according to aspect 3, wherein the polycarbonate copolymer component comprises isophthalate-terephthalate-resorcinol monomer units and bisphenol A monomer units, sebacic acid monomer units and bisphenol A monomer units, polycarbonate-siloxane copolymers, or combinations thereof.

[0097] Aspect 5. The thermoplastic composition according to aspect 4, wherein the polycarbonate copolymer component comprises about 0.1 mol% to about 10 mol% of sebacic acid monomer units and about 90 mol% to about 99.9 mol% of bisphenol A monomer units.

[0098] Aspect 6. The thermoplastic composition according to aspect 4, wherein the polycarbonate copolymer component comprises a polycarbonate-siloxane copolymer, and wherein the polycarbonate-siloxane copolymer has a siloxane content of about 5 wt% to about 45 wt%.

[0099] Aspect 7. The thermoplastic composition according to any one of aspects 1 to 6, wherein the core-shell acrylic polymer component comprises a siloxane.

[0100] Aspect 8. The thermoplastic composition according to any one of aspects 1 to 7, wherein the composition comprises greater than 0 wt% to about 50 wt% of the PBT component.

[0101] Aspect 9. The thermoplastic composition according to any one of aspects 1 to 8, wherein the composition comprises at least one additional additive.

[0102] Aspect 10. The thermoplastic composition according to aspect 9, wherein the at least one additional additive comprises an acid remover, an anti-drip 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, an impact modifier, a foaming agent, a reinforcing agent, or a combination thereof.

[0103] Aspect 11. The thermoplastic composition according to aspect 9 or 10, wherein the composition comprises about 0.1 wt% to about 8 wt% of the at least one additional additive.

[0104] Aspect 12. The thermoplastic composition according to any one of aspects 1 to 11, wherein the comparative tracking index (CTI) of the composition is CTI 600V as measured according to IEC 60112, or CTI PLC0 as measured according to ASTM D3638.

[0105] Aspect 13. The thermoplastic composition according to any one of Aspects 1 to 12, wherein the flexural modulus of the composition is at least 1.9 gigapascals (GPa) as measured according to ASTM D790 at a speed of 1.27 mm / min.

[0106] Aspect 14. The thermoplastic composition according to any one of Aspects 1 to 13, wherein the notched Åzo wave impact strength of the composition at 25°C is at least 650 J / m, as determined by ASTM D256.

[0107] Aspect 15. The thermoplastic composition according to any one of aspects 1 to 14, wherein the composition has a V0 flame retardant rating as tested according to UL94 at a thickness of 1.0 mm.

[0108] Aspect 16. The thermoplastic composition according to any one of aspects 1 to 15, wherein the composition has a flame retardant property of at least 0.9 p(FTP) as tested according to UL94 at a thickness of 1.0 mm.

[0109] Aspect 17. An article comprising the thermoplastic composition according to any one of aspects 1 to 16.

[0110] Aspect 18. The article of manufacture according to aspect 17, wherein the article of manufacture is an electrical connector, insulating housing, or insulating material for use in solar photovoltaic or electric vehicle or other electrical equipment components.

[0111] Example

[0112] The following examples are provided to provide a complete disclosure and description of how to manufacture and evaluate the compounds, compositions, articles, apparatus, and / or methods claimed herein, and are intended merely as examples and not to limit this disclosure. Efforts have been made to ensure the accuracy of figures (e.g., amounts, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise stated, parts are parts by weight, temperatures are in °C or at ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise specified, percentages of compositions refer to wt%.

[0113] Many variations and combinations of reaction conditions, such as component concentrations, desired solvents, solvent mixtures, temperature, pressure, and other reaction ranges and conditions, can be used to optimize the purity and yield of the product obtained from the process. Optimizing such process conditions requires only reasonable and routine experiments.

[0114] The compositions described herein include one or more components as described in Table 1:

[0115] Table 1 - Raw Materials

[0116]

[0117]

[0118] The pellets were compounded in a laboratory twin-screw extruder (Coperion ZSK-26Mc), with all components fed from the main feed inlet. Compounding was carried out at a screw speed of 200 rpm and a throughput of 20 kg / h. The temperature profiles for compounding are provided in Table 2.

[0119] Table 2 - Mixing Temperature Curve

[0120]

[0121] Various bars were injection molded on a FANUC S-2000i injection molding machine for tensile, flexural, impact, and CTI testing. Test bars for UL94 FR testing were molded using a Netstal SynErgy 1500k / 230 injection molding machine. Typical specimen injection conditions are provided in Table 3.

[0122] Table 3 - Typical Injection Molding Conditions for Samples

[0123]

[0124] Specific gravity was assessed according to ASTM D792. Melt flow rate (MFR) was assessed according to ASTM D1238 at 250°C and a 5.0 kg load. Tensile testing was assessed according to ASTM D638 at a speed of 50 mm / min. Bending testing was conducted according to ASTM D790 at a speed of 1.27 mm / min. Notched Electron impact resistance (NII) was assessed according to ASTM D256 at the temperature specified in the table (room temperature (RT) is 25°C). Flame retardancy (Vx) was assessed according to UL94 using 1.0 mm thick bars. FOT refers to flameout time. The p(FTP) value is a statistical assessment of the robustness of UL94 V0 performance. When the p(FTP) value is 1 or close to 1, the material is expected to consistently meet the UL94 V0 rating. CTI was assessed according to ASTM D3638.

[0125] The comparative and example compositions were prepared as shown in Tables 4A to 4D:

[0126] Table 4A – Example Compositions and Comparative Compositions

[0127]

[0128]

[0129] Table 4B – Example Compositions and Comparative Compositions

[0130]

[0131] Table 4C – Example Compositions and Comparative Compositions

[0132]

[0133] Table 4D – Example Compositions and Comparative Compositions

[0134]

[0135]

[0136] Various performance evaluations were performed on the compositions in Tables 4A to 4D; the results are shown in Tables 5A to 5D:

[0137] Properties of the compositions (Tables 5A-4A)

[0138]

[0139] Properties of compositions in Tables 5B-4B

[0140]

[0141] Properties of compositions in Tables 5C-4C

[0142]

[0143] Properties of the compositions in Tables 5D-4D

[0144]

[0145] Discussion of the results in Tables 5A to 5D:

[0146] Comparison of compositions C.01 and C.02 with Ex.01 and Ex.02 revealed that the use of FR-245 aromatic bromide and cyanurate FR agent provides high CTI performance from CTI PLC2 to CTI PLC0. Furthermore, Ex.01 and Ex.02 also exhibit high ozont impact resistance exceeding 650 joules / meter (J / m).

[0147] Comparison of C.01-C.05 with Ex.01-Ex.03 revealed that the silicone loading affects CTI performance; compositions with a total silicone loading of less than 1.5 wt% can maintain the CTI rating of PLC0.

[0148] Comparing C.06 and C.07 with Ex.03, the comparative compositions, including E-MA-GMA copolymers or E-GMA copolymers (AX8900 or AX8840) as impact modifiers, exhibited good CTI properties, but the flexural modulus of the comparative compositions was less than 1.9 gigapascals (1900 MPa), which limited the range of applications for such impact modifiers.

[0149] The example compositions Ex.04-Ex.12 vary in the content and type of impact modifier. These compositions exhibit good flame retardancy, CTI, modulus, and impact resistance.

[0150] The types and amounts of impact modifiers and PC copolymers in the example compositions Ex.13-Ex.15 vary. These compositions exhibit good flame retardancy, CTI, modulus, and impact resistance. In contrast, the comparative composition C.08, which includes brominated polycarbonate, has poorer impact resistance and CTI.

[0151] These results show that the following example compositions can achieve ideal performance: (1) brominated flame retardants comprising a combination of aromatic bromine and cyanurate; (2) acrylic core-shell impact modifiers; (3) compositions containing less than 2.0 wt% siloxane; said compositions can achieve CTI PLC0 or CTI 600V, a tensile modulus of at least 1.9 GPa, and a notched oz. impact strength of at least 650 J / m at room temperature.

[0152] Other comparative and example compositions were prepared as shown in Table 6A: various performance evaluations were performed on the compositions in Table 6A; the results are shown in Table 6B:

[0153] Table 6A – Example Compositions and Comparative Compositions

[0154]

[0155] Tables 6B-6A: Properties of the Compositions

[0156]

[0157] Example compositions Ex.16 and Ex.17 comprise an aromatic brominated and cyanurate flame retardant component (FR-245) and 40 wt% PBT (Ex.16) or no PBT (Ex.17). Comparative compositions C.09 and C.10 comprise brominated PC instead of FR-245 flame retardant. Each of these compositions comprises the same amount of bromine (6.7 wt%) in the total formulation.

[0158] The results in Table 6B unexpectedly show that the NII and CTI performance of example compositions Ex.16 and Ex.17 are improved compared to their respective comparative compositions C.09 and C.10. Therefore, according to various aspects of this disclosure, compositions including those with 40 wt% or higher PBT content, or even compositions containing no PBT at all, can achieve the ideal NII and CTI performance described herein.

[0159] 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, for instance, by those skilled 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 a 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 into the detailed description, 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 equivalents granted by such claims.

Claims

1. A thermoplastic composition comprising: The polycarbonate (PC) homopolymer component comprises approximately 35 wt% to approximately 65 wt%. 0 wt% to approximately 50 wt% of polybutylene terephthalate (PBT) component; About 5 wt% to about 20 wt% of a core-shell acrylic polymer component; and Aromatic brominated and cyanurate flame retardant components, from about 0.1 wt% to about 20 wt%. The total siloxane content of the composition is not greater than 2.0 wt%, and 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.

2. The thermoplastic composition according to claim 1, wherein the flame retardant component comprises tris(tribromophenyl)cyanurate.

3. The thermoplastic composition according to claim 1 or 2, wherein the composition further comprises a polycarbonate copolymer component of greater than 0 wt% to about 15 wt%.

4. The thermoplastic composition according to claim 3, wherein the polycarbonate copolymer component comprises isophthalate-terephthalate-resorcinol monomer units and bisphenol A monomer units, sebacic acid monomer units and bisphenol A monomer units, polycarbonate-siloxane copolymers, or combinations thereof.

5. The thermoplastic composition according to claim 4, wherein the polycarbonate copolymer component comprises about 0.1 mol% to about 10 mol% of sebacic acid monomer units and about 90 mol% to about 99.9 mol% of bisphenol A monomer units.

6. The thermoplastic composition of claim 4, wherein the polycarbonate copolymer component comprises a polycarbonate-siloxane copolymer, and wherein the polycarbonate-siloxane copolymer has a siloxane content of about 5 wt% to about 45 wt%.

7. The thermoplastic composition according to any one of claims 1 to 6, wherein the composition comprises greater than 0 wt% to about 50 wt% of the PBT component.

8. The thermoplastic composition according to any one of claims 1 to 7, wherein the core-shell acrylic polymer component comprises a siloxane.

9. The thermoplastic composition according to any one of claims 1 to 8, wherein the composition comprises at least one additional additive, said at least one additional additive comprising an acid remover, an anti-drip 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, an impact modifier, a foaming agent, a reinforcing agent, or a combination thereof.

10. The thermoplastic composition of claim 9, wherein the composition comprises about 0.1 wt% to about 8 wt% of the at least one additional additive.

11. The thermoplastic composition according to any one of claims 1 to 10, wherein the comparative tracking index (CTI) of the composition is CTI 600V as measured according to IEC 60112, or CTI PLC0 as measured according to ASTM D3638.

12. The thermoplastic composition according to any one of claims 1 to 11, wherein the flexural modulus of the composition is at least 1.9 gigapascals (GPa) as measured according to ASTM D790 at a speed of 1.27 mm / min.

13. The thermoplastic composition according to any one of claims 1 to 12, wherein the notched Åzo wave impact strength of the composition at 25°C is at least 650 J / m, as determined by ASTM D256.

14. The thermoplastic composition according to any one of claims 1 to 13, wherein the composition has a V0 flame retardancy rating as tested according to UL94 at a thickness of 1.0 mm, or has a p(FTP) flame retardancy of at least 0.9 as tested according to UL94 at a thickness of 1.0 mm.

15. An article comprising the thermoplastic composition according to any one of claims 1 to 14, wherein the article is an electrical connector, an insulating housing, an insulating material for solar photovoltaic or electric vehicles, or another electrical equipment component.

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