PFAS-free flame retardant, impact resistant and chemical resistant polycarbonate compositions

Abstract

Polycarbonate compositions include: a. from 20 wt% to 93 wt% of a polycarbonate component including one or more of a virgin polycarbonate homopolymer and a post- consumer recycled polycarbonate; b. from 1 wt% to 25 wt% of a polycarbonate-polysiloxane copolymer having (1) a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and (2) a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and c. from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive. The flame retardant additive is free of or substantially free of halogen. A molded sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 mm or less.

Description

PFAS-FREE FLAME RETARDANT, IMPACT RESISTANT AND CHEMICAL RESISTANT POLYCARBONATE COMPOSITIONSFIELD OF THE DISCLOSURE

[0001] The present disclosure relates to materials including polycarbonate compositions, and in particular to polycarbonate compositions exhibiting improved environmental stresscracking chemical resistance and processability while maintaining flame performance.BACKGROUND

[0002] Polycarbonate (PC) polymers are useful materials in the manufacture of articles and components for a wide range of applications. Because of their broad use, particularly in the electronics market, it is desirable to provide polycarbonate compositions with excellent physical, optical, and thermal properties in an adequate processing window. Such properties may be particularly difficult to achieve in thin-wall applications. Polycarbonate / acrylonitrile butadiene styrene (PC / ABS) blends are polycarbonate thermoplastic compositions that are widely used in electronics applications. Though generally resilient, these polycarbonate composition blends may also be susceptible to fracture or breakage upon exposure to various chemical media even at relatively low stress levels. In addition, more stringent regulations are being enacted to reduce or eliminate the presence of halogens, in particular fluorine, in endproducts, and to encourage the use of more sustainable materials such as recycled PC.

[0003] Accordingly, there remains a need for thermoplastic compositions having improved environmental stress-cracking chemical resistance, impact, and comparable FR performance without using halogen additives, which may also apply to compositions including higher loading of post-consumer recycled polycarbonates.SUMMARY

[0004] Aspects of the disclosure relate to polycarbonate compositions including: a. from 20 wt% to 93 wt% of a polycarbonate component including one or more of a virgin polycarbonate homopolymer and a post-consumer recycled polycarbonate; b. from 1 wt% to 25 wt% of a polycarbonate-polysiloxane copolymer having (1) a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and (2) a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and c. from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive. The flame retardant additive is freeof or substantially free of halogen. A molded sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

[0005] The above described and other features are exemplified by the following detailed description, examples, and claims.BRIEF DESCRIPTION OF FIGURES

[0006] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects and together with the description serve to explain the principles of the of the disclosure.

[0007] FIG. 1 presents Table 1 showing the materials used to prepare comparative and example formulations.

[0008] FIG. 2 presents Table 4 showing formulations Cl.l to C3.1 and El.l to E3.3.

[0009] FIG. 3 presents Table 5 showing the properties and the applicable testing standards.

[0010] FIG. 4 presents Table 6 showing the criteria for flame retardant performance V-0.

[0011] FIG. 5 presents Table 7 showing the criteria for environmental stress-cracking chemical resistance.

[0012] FIG. 6 presents Table 8 showing the observed properties for the comparative samples and example formulations of FIG. 2 (Table 4).DETAILED DESCRIPTION OF ILLUSTRATIVE ASPECTS

[0013] The present disclosure may be understood more readily by reference to the following detailed description of desired aspects and the examples included therein. In the following specification and the claims that follow, reference will be made to a number of terms which have the following meanings. Also, within the scope of the disclosure are articles of manufacture prepared according to any of the methods described herein. For example, articles that can be produced using the materials and methods of the disclosure include those in the electrical field.

[0014] There accordingly remains a need in the art for flame retardant polycarbonate compositions suitable for thin- wall applications. It would be a further advantage if the compositions were essentially halogen-free.

[0015] Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic and electrical appliances. For example, polycarbonate blends including polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) are widely used materials in the consumer electronics market including, but not limited to, TV frames, computer peripherals, mobile phone housings / cases, and device enclosures. Although these materials are generally durable, they are susceptible tocatastrophic brittle failure at relatively low stress in certain environments and upon exposure to certain substances. To achieve thin-walled flame retardantV-0 performance typically required for the consumer electronics market, per- and polyfluoroalkyl substances (PFAS) are often added as an anti-dripping agent. These PFAS however face increasing global scrutiny for negative environmental impact. Further global concern on electronic product waste or “e- waste” and an emphasis on sustainability has also led to an increased desire for recycled plastics.

[0016] Post-Consumer Recycled (PCR) plastic resins are increasingly used in the production of consumer electronics, which has also increased the demand for PCR PC / ABS materials for the electronics industry. However, high loadings (namely, greater than 30 wt%) of recycled content may reduce the mechanical integrity of the materials and ultimately make the blends more susceptible to environmental stress cracking and fatigue-related part failures.

[0017] Investigators have disclosed other PC formulations polycarbonate / ABS resins applications. U.S. Patent No. US 7,994,248 B2 discloses polycarbonate compositions exhibiting an improved combination of properties, particularly Vicat softening temperature and high flame retardance in thin wall applications.

[0018] Published U.S. Patent App. No. US 20130313493 Aldiscloses post-consumer recycled polycarbonate compositions hat can be lighter in weight and offer a balanced mechanical property including flame retardance.

[0019] U.S. Patent No. 9,018,286 B2 discloses flame retardant composition including a polycarbonate composition, an impact modifier, and a flame retardant (phosphazene). The compositions exhibit improved heat resistance, while maintaining good impact properties, flame retardance, ductility, and melt stability.

[0020] Published International Patent Application No. WO 2019123029 Aldiscloses compositions including a polycarbonate-polysiloxane copolymer exhibiting improved chemical resistance in blends with PC.

[0021] There have been other attempts to address polycarbonate compositions with improved flame performance, chemical resistance, and sufficient ductility. Published International Patent Application No. WO 2022107030 Al discloses polycarbonate and polyester blend compositions exhibiting flame performance. Published International Patent Application No. WO 2022107029 Al discloses combinations of polycarbonate and polyester that achieve chemical resistance and flame performance.

[0022] Compositions of the present disclosure overcome existing shortcomings of conventional PC / ABS materials. The disclosed formulations achieve - PFAS free flameretardant, improved impact and environmental stress cracking resistant solutions with other properties comparable to typical PC / ABS.

[0023] The disclosed compositions combine polycarbonates (either virgin or with PCR PC) were blended with BPADP (or other phosphorous FR agents such as PPZ) and a polycarbonate-polysiloxane copolymer to provide PFAS free flame performance and excellent environmental stress-cracking chemical resistance while maintaining mechanical performance.

[0024] Aspects of the present disclosure may resolve many of the above-described technical limitations associated with flame retardant polycarbonate compositions, particularly flame retardant polycarbonate compositions including a post-consumer recycled polycarbonate polymer.

[0025] Compositions according to aspects of the disclosure exhibit improved properties as compared to conventional flame retardant polycarbonate compositions. As provided herein, improved properties include, but are not limited to, environmental stress-cracking chemical resistance, mechanical properties such as impact strength, as well as colorability, and a UL- 94 rating ofV-0 at a thickness of 1.5 millimeters or less.

[0026] The disclosed compositions may include from about 20 wt% to 93 wt% of a polycarbonate component including one or more of: a virgin polycarbonate homopolymer, and a post-consumer recycled polycarbonate; from 1 wt% to 25 wt% of a polycarbonate- polysiloxane copolymer having a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive. The combined weight percent value of all components does not exceed 100 wt%, all weight percent values are based on the total weight of the composition.

[0027] Before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Various combinations of elements of this disclosure are encompassed by this disclosure, for example, combinations of elements from dependent claims that depend upon the same independent claim.

[0028] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.Polycarbonate Compositions

[0029] Polycarbonate compositions according to aspects of the disclosure include: a. from 20 wt% to 93 wt% of a polycarbonate component including one or more of a virgin polycarbonate homopolymer and a post-consumer recycled polycarbonate; b. from 1 wt% to 25 wt% of a polycarbonate-polysiloxane copolymer having (1) a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and (2) a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and c. from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive. The flame retardant additive is free of or substantially free of halogen. A molded sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less. The combined weight percent value of all components does not exceed 100 wt%, all weight percent values are based on the total weight of the composition.

[0030] In further aspects, a molded sample of the composition may exhibit improved environmental stress-cracking chemical resistance, as tested in accordance with ASTM D543, as compared to a reference composition that includes a fluoropolymer or that includes a polycarbonate-polysiloxane copolymer that has a siloxane content of less than 30 wt% or greater than 70 wt%.

[0031] The polycarbonate component may include a mixture of polycarbonate homopolymers or a mixture of PCR polycarbonate resins derived from multiple sources. In some aspects, the polycarbonate-polysiloxane copolymer has a weight average molecular weight of 30,000 to 45,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0032] Compositions according to aspects of the disclosure have improved properties ascompared to a polycarbonate composition including a PFAS flame retardant anti -drip agent or that includes a polycarbonate-polysiloxane copolymer or that has a siloxane content of less than 30 wt% or greater than 70 wt%. Improved properties include, but are not limited to, environmental stress-cracking chemical resistance, flame performance and colorability.

[0033] In certain aspects, a molded sample including the composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

[0034] As the flame retardant additive is free of or substantially free of halogen, the polycarbonate may similarly be free of added halogen in certain aspects.Polycarbonate Component

[0035] In various aspects, the disclosed polycarbonate composition includes a polycarbonate component including one or more of a virgin polycarbonate polymer and a PCR polycarbonate polymer. As used herein, polycarbonate may define any polycarbonate material or mixture of materials, for example, as recited in U.S. Patent No. 7,786,246, which is hereby incorporated in its entirety for the specific purpose of disclosing various polycarbonate compositions and methods. The term polycarbonate can be further defined as compositions having repeating structural units of the formula (1):in which at least 60 percent of the total number of R1groups are aromatic organic radicals and the balance thereof are aliphatic, alicyclic, or aromatic radicals. In a further aspect, each R1is an aromatic organic radical and, more preferably, a radical of the formula (2):— A1— Y1— A2— (2), wherein each of A1and A2is a monocyclic divalent aryl radical and Y1is a bridging radical having one or two atoms that separate A1from A2. In various aspects, one atom separates A1from A2. For example, radicals of this type include, but are not limited to, radicals such as — O— , — S— , — S(O) — , — S(O2) — , — C(O) — , methylene, cyclohexyl-methylene, 2-[2.2.1]- bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene. The bridging radical Y1is preferably a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.

[0036] In various further aspects, “polycarbonates” and “polycarbonate resins” as used herein further defines homopolycarbonates (referred to herein as “polycarbonate homopolymers,” having the same R1), copolymers including different R1moieties in the carbonate (referred to herein as “copolycarbonates” or “polycarbonate copolymers”),copolymers including carbonate units and other types of polymer units, such as ester units, poly siloxane units, and combinations including at least one of polycarbonate homopolymers and polycarbonates copolymers. As used herein, “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0037] In specific aspects, the disclosed polycarbonate composition includes from about 20 wt% to about 93 wt% of the polycarbonate component. In further aspects the composition includes at least 20 wt%, or at least 25 wt%, or 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 least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at most 93 wt%, or at most 90 wt%, or at most 85 wt%, or at most 80 wt%, or at most 75 wt%, or at most 70 wt%, of the polycarbonate component.

[0038] The polycarbonate component may include one or more of a virgin polycarbonate homopolymer and a post-consumer recycled polycarbonate.

[0039] According to various aspects, the polycarbonate component may include a mixture of polycarbonate homopolymers. The polycarbonate component may include a polycarbonate homopolymer having a weight average molecular weight of at least 20,000 grams per mole (g / mol) as determined by gel permeation chromatography (GPC) using polystyrene standards and calculated for polycarbonate. For example, the polycarbonate homopolymer may have a weight average molecular weight of 20,000 grams per mole to 35,000 grams per mole. In yet further examples, the disclosed composition may include a first polycarbonate homopolymer having a weight average molecular weight of 19,000 to 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a second polycarbonate homopolymer having a weight average molecular weight of 29,000 to 32,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof. A first polycarbonate homopolymer may have a molecular weight of from about 20,000 g / mol to 22,000 g / mol determined by GPC using BPA homopolycarbonate standards. A second polycarbonate homopolymer may have a molecular weight of from about 30,000 g / mol to 31,000 g / mol determined by GPC using BPA homopolycarbonate standards.

[0040] Virgin polycarbonate homopolymer may be present in the disclosed polycarbonate composition in an amount from about 20 wt% to about 93 wt% and within the ranges provided above. PCR PC may be present in the disclosed polycarbonate composition in an amount from about 20 wt% to about 93 wt% and within the ranges provided above. If the composition includes both a virgin polycarbonate homopolymer and a PCR PC, eachcomponent may individually be present in the composition in an amount of from 5 wt% to 93 wt%. In further aspects, the composition includes each of these components in an amount of at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or 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 least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at most 93 wt%, or at most 90 wt%, or at most 85 wt%, or at most 80 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%, or at most 50 wt%, or at most 45 wt%, or at most 40 wt%, or at most 35 wt%, or at most 30 wt%, or at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most 10 wt%.

[0041] As provided herein, the polycarbonate component may include post-consumer recycled polycarbonate. PCR PC may be reclaimed from post-consumer sources, including but not limited to, water bottles, home appliances waste for example TV, air-conditioners, washing machines, refrigerators, and the like. Virgin may refer to a polymer that has not been used in end-use parts, articles, or components. Regardless of the source, the PCR PC components may be similar or even identical to those virgin plastic components, known as impact modifier components, that are conventionally used in the manufacture of impact modified thermoplastic blend compositions. However, an important difference between virgin plastic components and recycled plastics utilized in the present compositions, is the presence of at least one impurity that is not present in a virgin material. For example, one or more additives conventionally used in the manufacture of impact modified thermoplastics can be present as an impurity. Additional impurities may include processing residues such as lubricants, mold release agents, antistatic agents, stabilizers, light stabilizers, flame retardants, metals (for example, iron, aluminum, and copper). Still further, the impurities can include polyurethane particles that cannot be fully removed during the recycling process. In certain aspects, a PCR polycarbonate may be distinguished from a virgin polycarbonate by the inclusion of at least 10 mol% -OH endgroup content in the polycarbonate. In some aspects, the PCR polycarbonate includes from 10 mol% to 35 mol% -OH endgroup content in the polycarbonate.

[0042] In some aspects, the recycled PC may be clear or colored. Clear recycled PC may be sourced from, for example, water bottles, recycled PC sheets, automobile headlights, and optical discs (e.g., one or more of compact discs (CDs), digital versatile discs (DVDs) and Blue-ray discs). The PCR PC may be optical quality. A suitable source for colored PCR PC is water bottles. The polycarbonate component may include a mixture of post-consumerrecycled polycarbonate from multiple sources. For example, the composition may include a PCR PC derived from water bottles and a PCR PC derived from CDs. In certain aspects the PCR PC may be transparent. For example, the polycarbonate composition may include a PCR PC derived from transparent plastic having a light transmittance of greater than 82% at a thickness of 3 mm as determined in accordance with ASTM DI 003.Polycarbonate-Polysiloxane Copolymer

[0043] In various aspects, the disclosed polycarbonate compositions may further include a polycarbonate-polysiloxane copolymer. Non-limiting examples of polysiloxanepolycarbonate copolymers can include various copolymers available from SABIC™. As used herein, the term polycarbonate-polysiloxane copolymer may refer to LEXAN™ EXL- polycarbonate resin or LEXAN™ resin (commercially available from SABIC™) according to the content of siloxane in the polycarbonate-polysiloxane copolymer.

[0044] In certain aspects the polysiloxane-polycarbonate copolymer having a siloxane content of from about 30 wt% to about 70 wt% is present in the composition in an amount of from 1 wt% to 25 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 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 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 most 25 wt%, or at most 24 wt%, or at most 23 wt%, or at most 22 wt%, or at most 21 wt%, or at most 20 wt%, or at most 19 wt%, or at most 18 wt%, or at most 17 wt%, or at most 16 wt%, or at most 15 wt%, or at most 14 wt%, or at most 13 wt%, or at most 12 wt%, or at most 11 wt%, or at most 10 wt%, or at most 9 wt%, or at most 8 wt%, or at most 7 wt%, or at most 6 wt%, or at most 5 wt%.

[0045] Polycarbonate-polysiloxane copolymers may be useful polycarbonate copolymers and may include 30 wt% to 70 wt% of carbonate units and 30 wt% to 70 wt% siloxane units; this may also be referred to as a polycarbonate-polysiloxane copolymer having a siloxane content of from 30 wt% to 70 wt%. Within this range, in some aspects the polycarbonate- polysiloxane copolymer has a siloxane content of at least 30 wt%, or at least 35 wt%, or at least 38 wt%, or about 40 wt%, or at least 42 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 70 wt%, or at most 65 wt%, or at most 60 wt%, or at most 55 wt%, or at most 50 wt%, or at most 45 wt%, or at most 42 wt%, or at most 40 wt%, or at most 35 wt%. The balance of the polycarbonate-polysiloxane copolymer is carbonate units.

[0046] In specific aspects, the polycarbonate-polysiloxane copolymer has a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%. In further aspects, the composition has a total siloxane content of at least 0.5 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 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 most 25 wt%, or at most 20 wt%, or at most 19 wt%, or at most 18 wt%, or at most 17 wt%, or at most 16 wt%, or at most 15 wt%, or at most 14 wt%, or at most 13 wt%, or at most 12 wt%, or at most 11 wt%, or at most 10 wt%, or at most 9 wt%, or at most 8 wt%, or at most 7 wt%, or at most 6 wt%, or at most 5 wt%, or at most 4.5 wt%, or at most 4 wt%, or at most 3.5 wt%, or at most 3 wt%.

[0047] The disclosed polycarbonate-polysiloxane copolymer having a siloxane content of from about 30 wt% to 70 wt% may have a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate. In yet further examples, the polycarbonate- polysiloxane copolymer having a siloxane content of from 30 wt% to 70 wt% has a weight average molecular weight of 30,000 to 45,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0048] In various aspects, the polycarbonate composition may include a polycarbonate- polysiloxane copolymer having 40 wt% polysiloxane content based upon the total weight of the polysiloxane-polycarbonate copolymer. In various aspects, the 40 wt% polysiloxane block copolymer may have a weight average molecular weight (Mw) of from about 26,000 to 50,000 g / mol as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0049] In some aspects, polycarbonate further includes a polysiloxane-polycarbonate copolymer having a siloxane content of from about 0.5 wt% to about 30 wt%. The polycarbonate-polysiloxane copolymer having a siloxane content of from about 0.5 wt% to about 30 wt% may be present in an amount effective to provide the composition with a total siloxane content of 1 wt% to 25 wt%.

[0050] In certain aspects the polysiloxane-polycarbonate copolymer having a siloxane content of from about 0.5 wt% to about 30 wt% is present in the composition in an amount of from 1 wt% to 25 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4wt%, 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 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 most 25 wt%, or at most 24 wt%, or at most 23 wt%, or at most 22 wt%, or at most 21 wt%, or at most 20 wt%, or at most 19 wt%, or at most 18 wt%, or at most 17 wt%, or at most 16 wt%, or at most 15 wt%, or at most 14 wt%, or at most 13 wt%, or at most 12 wt%, or at most 11 wt%, or at most 10 wt%, or at most 9 wt%, or at most 8 wt%, or at most 7 wt%, or at most 6 wt%, or at most 5 wt%.

[0051] In one example, the polycarbonate composition may further include a polycarbonate-polysiloxane copolymer having from 4-8 wt%, or 5-7 wt%, or about 6 wt% polysiloxane content based upon the total weight of the polysiloxane-polycarbonate copolymer. In various aspects, a 6 wt% polysiloxane block copolymer has a weight average molecular weight (Mw) of from about 23,000 to 24,000 Daltons using gel permeation chromatography with a bisphenol A polycarbonate absolute molecular weight standard. In certain aspects, the 6 wt% siloxane polysiloxane-polycarbonate copolymer has a melt volume flow rate (MVR) of about 10 cm3 / 10 min at 300 °C / 1.2 kg (see C9030T, a 6 wt% polysiloxane content copolymer available from SABIC™ as “transparent” EXL C9030T resin polymer). In another example, the polysiloxane-polycarbonate block can include from 18-22 wt%, or 19-21 wt%, or about 20 wt% polysiloxane based upon the total weight of the polysiloxane block copolymer. In a further example, an additional appropriate polysiloxane- polycarbonate copolymer may be a bisphenol A polysiloxane-polycarbonate copolymer endcapped with para-cumyl phenol (PCP) and having a 20% polysiloxane content (commercially available from SABIC as the “opaque” EXL or C9030P). In various aspects, the weight average molecular weight of the 20 wt% poly siloxane block copolymer is about 29,900 Daltons to about 31,000 Daltons when tested according to a polycarbonate standard using gel permeation chromatography (GPC) on a cross-linked styrene -di vinylbenzene column and calibrated to polycarbonate references using a UV-VIS detector set at 264 nanometers (nm) on 1 milligram per milliliter (mg / ml) samples eluted at a flow rate of about 1.0 ml / minute. Moreover, the 20% polysiloxane block copolymer has a melt volume rate (MVR) at 300 °C / 1.2 kg of 7 cm3 / 10 min and can exhibit siloxane domains sized in a range of from about 5 microns (pm) to about 20 pm.

[0052] Representative polycarbonate-polysiloxane copolymers include those exemplified within this specification. In some aspects, two or more polycarbonate-polysiloxane copolymers may be used. For example, in some aspects, blends of end-capped and hydroxyterminated materials may be used. In other aspects, blends of similar chemistries having different proportions of siloxane may also be used. The polycarbonate composition may further include a polycarbonate homopolymer or a polycarbonate copolymer different from the polycarbonate -poly siloxane copolymer.

[0053] The disclosed polycarbonate -poly siloxane copolymer block copolymers can also be end-capped. For example, according to aspects of the disclosure, a polycarbonate - polysiloxane copolymer block copolymer is end capped with p-cumyl -phenol.Flame retardant additive

[0054] In some aspects the composition includes from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive. The flame retardant additive is free of or substantially free of halogen.

[0055] In certain aspects the composition includes greater than 6 wt%, or at least 6.5 wt%, or at least 7 wt%, or at least 8 wt%, or at least 9 wt%, or at least 10 wt%, or at least 11 wt%, or at least 12 wt%, or at most 20 wt%, or at most 19 wt%, or at most 18 wt%, or at most 17 wt%, or at most 16 wt%, or at most 15 wt%, or at most 14 wt%, or at most 13 wt%, or at most 12 wt%, or at most 11 wt%, or at most 10 wt%, or at most 9 wt%, of the phosphorous flame retardant additive.

[0056] Suitable phosphorus flame retardant additives include organic compounds that include phosphorus such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0057] In further aspects, the flame retardant additive or a portion thereof includes an organic phosphate and / or an organic compound containing a phosphorus-nitrogen bond. In one aspect, suitable flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(aziridinyl)phosphine oxide. In further other aspects, the flame retardant can include a mixture of two or more individual flame retardant compositions.

[0058] A suitable organic phosphate is an aromatic phosphate of the formula (GO)3P=O, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl group, provided that at least one G is an aromatic group. Two of the G groups can be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate. Exemplary aromatic phosphates include, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)phosphate, phenyl bis(3,5,5’-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p- tolyljphosphatc. bis(2-ethylhexyl)p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5’- trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, or the like.

[0059] In further aspects, the flame retardant is selected from oligomeric phosphate, polymeric phosphate, oligomeric phosphonate, ammonium polyphosphate (Exolit OP) or mixed phosphate / phosphonate ester flame retardant compositions. The flame retardant may include triphenyl phosphate, cresyldiphenylphosphate, tri(isopropylphenyl)phosphate, resorcinol bis(diphenylphosphate), and bisphenol-A bis(diphenyl phosphate). As an example, the flame retardant may include bisphenol A bis(diphenyl phosphate) (BPADP).

[0060] In specific aspects the phosphorous flame retardant additive includes bisphenol A diphenyl phosphate (BPADP), phenoxycyclophosphazene (PPZ), or combinations thereof.

[0061] As provided herein, the flame retardant additive is non-halogenated or may be considered free of or substantially free of halogen or added halogen. The disclosed polycarbonate compositions may have a UL-94 flame test rating of V-0 at a thickness of 1.5 mm or thinner and be considered “essentially halogen-free” “substantially free of halogen” or “halogen free” per IEC 61249-2-21 or UL 746H. As used herein, the phrase “essentially halogen-free” is as defined by IEC 61249-2-21 or UL 746H. According to International Electrochemical Commission, Restriction Use of Halogen (IEC 61249-2-21), a composition should include 900 parts per million (ppm) or less of each of chlorine and bromine and also include 1500 ppm or less of total bromine, chlorine, and fluorine content. According to UL 746H, a composition should include 900 ppm or less of each of chlorine, bromine, and fluorine and 1500 ppm or less of the total chlorine, bromine, and fluorine content.

[0062] Accordingly, the disclosed composition may exhibit a calculated added bromine and added chlorine content that are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition that is about 1500 ppm or less. In further aspects, the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition may each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition may be about 1500 ppm or less. In specific aspects, the polycarbonate composition includes 1000 ppm or less of added fluorine based on the total content of the composition.

[0063] In some aspects the phosphorus flame retardant additive is a liquid additive.

[0064] In particular aspects compositions including greater than 6 wt% of the phosphorous flame retardant additive allows for the composition to have good flow (MVR) propertieswhile maintaining UL 94 VO performance. Use of a liquid phosphorous flame retardant additive can further improve the MVR performance of the composition.Additives

[0065] The composition can include various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the thermoplastic composition (good compatibility for example). Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. The total amount of all of the additives in the resin composition is, for example, 0.001 to 10 wt% based on the total weight of the composition. Suitable additives can include, but are not limited to an acid scavenger, antioxidant, antistatic agent, chain extender, colorant, de-molding agent, flow promoter, lubricant, mold release agent, plasticizer, quenching agent, flame retardant, ultraviolet (UV) reflecting additive, or a combination thereof.

[0066] In some aspects the composition includes at least 0.001 wt%, or at least 0.01 wt%, or 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 1.0 wt%, or at least 1. 1 wt%, or at least 1.2 wt%, or at least 1.3 wt%, or at least 1.4 wt%, or at least 1.5 wt%, or at most 10 wt%, or at most 9 wt%, or at most 8 wt%, or at most 7 wt%, or at most 6 wt%, or at most 5 wt%, or at most 4 wt%, or at most 3 wt%, or at most 2 wt%, or at most 1.5 wt%, or at most 1.4 wt%, or at most 1.3 wt%, or at most 1.2 wt%, or at most 1. 1 wt%, or at most 1.0 wt%, or at most 0.9 wt%, or at most 0.8 wt%, or at most 0.7 wt%, or at most 0.6 wt%, or at most 0.5 wt%, of at least one additional additive.

[0067] In certain aspects, the disclosed compositions may include an anti-drip agent, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti -drip agent can be encapsulated by a rigid copolymer, for example styreneacrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. A TSAN includes 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can include, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer.

[0068] In certain aspects the composition includes from 0.01 wt% to 2 wt% of an anti-drip agent. In particular aspects the composition includes at least 0.01 wt%, or 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 most 2 wt%, or at most 1.9 wt%, or at most 1.8 wt%, or at most 1.7 wt%, or at most 1.6 wt%, or at most 1.5 wt%, or at most 1.4 wt%, or at most 1.3 wt%, or at most 1.2wt%, or at most 1. 1 wt%, or at most 1.0 wt%, or at most 0.9 wt%, or at most 0.8 wt%, or at most 0.7 wt%, of the anti-drip agent.

[0069] In certain aspects the at least one additional additive is an impact modifier. The impact modifier is a chemically reactive impact modifier in some aspects. By definition, a chemically reactive impact modifier has at least one reactive group such that when the impact modifier is added to a polymer composition, the impact properties of the composition (expressed in the values of the Izod impact) are improved. In some examples, the chemically reactive impact modifier may be an ethylene or propylene-based homo- or copolymer with reactive functional groups selected from, but not limited to, anhydride, carboxyl, hydroxyl, and epoxy. In other examples, the chemically reactive impact modifier is an unhydrogenated or hydrogenated styrenic block copolymer grafted with reactive functional groups including, but not limited to, anhydride, carboxyl, hydroxyl, and epoxy.

[0070] In further aspects of the present disclosure, the composition can include a rubbery impact modifier. The rubber impact modifier can be a polymeric material which, at room temperature, is capable of recovering substantially in shape and size after removal of a force. However, the rubbery impact modifier should typically have a glass transition temperature of less than 0° C. In certain aspects, the glass transition temperature (Tg) is less than -5° C, -10° C, -15° C, with a Tg of less than -30° C typically providing better performance.Representative rubbery impact modifiers can include, for example, functionalized polyolefin ethylene-acrylate terpolymers, such as ethylene -acrylic esters- maleic anhydride (MAH) or glycidyl methacrylate (GMA). The functionalized rubbery polymer can optionally contain repeat units in its backbone which are derived from an anhydride group containing monomer, such as maleic anhydride. In another scenario, the functionalized rubbery polymer can contain functional moieties which are grafted onto the polymer in a post polymerization step.

[0071] In various aspects, the impact modifier may include a block copolymer grafted with at least one functional group. These functional groups may include, but are not limited to, carboxylic acid, anhydride, glycidyl group and their derivatives. In certain aspects, the impact modifier includes a styrenic block copolymer. For example, the block copolymer may include a styrene-based block copolymer such as a styrene-butadiene-styrene (SBS) copolymer, styrene-ethylene-butadiene-styrene (SEBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene ethylene-propylene-styrene (SEPS) copolymer, or styrene-fethylene- (ethylene-propylene)] -styrene (SEEPS) or a combination thereof.

[0072] In certain aspects the composition includes from 0.01 wt% to 5 wt% of an impact modifier. In particular aspects the composition includes at least 0.01 wt%, or 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 most 5 wt%, or at most 4 wt%, or at most 3 wt%, or at most 2 wt%, or at most 1.5 wt%, or at most 1 wt%, of the impact modifier.Methods of Manufacture

[0073] Aspects of the disclosure further relate to methods for making a thermoplastic composition. The one or any foregoing components described herein may be first dry blended with each other, or dry blended with any combination of foregoing components, then fed into an extruder from one or multi-feeders, or separately fed into an extruder from one or multifeeders. The fillers used in the disclosure may also be first processed into a masterbatch, then fed into an extruder. The components may be fed into the extruder from a throat hopper or any side feeders.

[0074] The extruders used in the disclosure may have a single screw, multiple screws, intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations including at least one of the foregoing.

[0075] The components may also be mixed together and then melt-blended to form the thermoplastic compositions. The melt blending of the components involves the use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations including at least one of the foregoing forces or forms of energy. The barrel temperature on the extruder during compounding can be set at the temperature where at least a portion of the polymer has reached a temperature greater than or equal to about the melting temperature, if the resin is a semi -crystalline organic polymer, or the flow point (for example, the glass transition temperature) if the resin is an amorphous resin.

[0076] The mixture including the foregoing mentioned components may be subject to multiple blending and forming steps if desirable. For example, the thermoplastic composition may first be extruded and formed into pellets. The pellets may then be fed into a molding machine where it may be formed into any desirable shape or product. Alternatively, the thermoplastic composition emanating from a single melt blender may be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0077] The temperature of the melt in the present process may in some aspects bemaintained as low as possible in order to avoid excessive thermal degradation of the components. In certain aspects the melt temperature is maintained between about 230°C and about 350°C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept relatively short. In some aspects, the melt processed composition exits processing equipment such as an extruder through small exit holes in a die. The resulting strands of molten resin may be cooled by passing the strands through a water bath. The cooled strands can be chopped into pellets for packaging and further handling.

[0078] In certain aspects, the blends may be processed using a clean compound solution where the materials are compounded in deionized water.

[0079] Methods may further include processing the composite to provide a plaque of a desired thickness. Plaques can be extruded, injection molded, compression molded, or injection-compression molded, and may have a thickness between about 0.4 mm and 6 mm. Other processes could also be applied to the thin thermoplastic film, including but not limited to, lamination, co-extrusion, thermo-forming or hot pressing. In such aspects, further layers of other materials (for example, other thermoplastic polymer layers, metallic layers, etc.) could be combined with the composite.Properties and Articles

[0080] As TSAN and other per- and polyfluoroalkyl substances (PFAS) face global environmental scrutiny, the addition of TSAN to improve conventional FR materials for electronic market applications is less desirable. Moreover, with growing concerns of e-waste, consumer electronic industry demand continues to trend toward the inclusion of more recycled materials such as PCR PC. Recycled materials including PCR PC however are plagued by colorability concerns and mechanical failure at higher recycled content loadings. Classical PC / ABS used in this industry is considered resilient, however these materials may become brittle when exposed to certain environments or chemical media at low stress. Consumer electronics are often exposed to skin oils (like moisturizer or sebum), sunscreen, and other cosmetics such as moisturizer or insect repellant, which can contribute to catastrophic brittle fracture of a polymer over time with exposure.

[0081] The disclosed polycarbonate compositions may overcome the shortcomings associated with some PC / ABS (and other PC compositions) that experience sudden breakage or fracture (brittle failure) at relatively low stress levels with exposure to certain chemical environments or media. Conventionally, ABS may be used as an impact modifier and flow enhancer for PC / ABS blends. Compositions of the present disclosure incorporating apolycarbonate-polysiloxane copolymer having a siloxane content of from 30 wt% to 70 wt% may exhibit similar melt characteristics (lower processing temperature than PC) compared with PC / ABS blends. However, the disclosed compositions having a polycarbonate- polysiloxane copolymer having a siloxane content of from 30 wt% to 70 wt%, rather than an ABS impact modifier, may exhibit better impact performance and environmental stresscracking chemical resistance compared to conventional PC / ABS formulations.

[0082] The disclosed compositions may also exhibit desirable flame retardant performance for electrical applications. The disclosed compositions may exhibit sufficient thin-walled flame retardant performance with our without fluoropolymer anti-drip agents such as (per- and polyfluoroalkyl substances (PFAS)). And, with growing global concerns on environmental waste and an emphasis on sustainability, the disclosed polycarbonate compositions may include higher loadings of post-consumer recycled PC without sacrificing colorability, mechanical, or flame performance.

[0083] Compositions of the present disclosure may exhibit PFAS free flame retardant performance, impact resistance and environmental stress cracking resistance with balanced properties of processibility and colorability.

[0084] In various aspects, the disclosed polycarbonate compositions exhibit improved environmental stress-cracking chemical resistance (ESCR) performance when tested in accordance with ASTM D543 for sunscreen, insect repellant, and / or sebum as chemical media. The improvement in ESCR performance is compared to a reference composition that includes a fluoropolymer or that includes a polycarbonate-polysiloxane copolymer that has a siloxane content of less than 30 wt% or greater than 70 wt%.

[0085] In some aspects improved ESCR performance means that the disclosed compositions achieve at least 90% tensile yield strength oyretention in sunscreen, insect repellant, and / or sebum (observed at 0.5% strain, 23 °C, 3 days). In further aspects improved ESCR performance means that the composition achieves at least 75-139%, or in specific aspects at least 80-139%, tensile elongation at break Ebr retention in sunscreen, insect repellant, and / or sebum (observed at 0.5% strain, 23 °C, 3 days). For example, the disclosed compositions may achieve at least 95% retention of tensile elongation at break (Ebr) in sunscreen (observed at 0.5% strain, 23 °C, 3 days) and at least about 90% or at least about 100% retention Ebr in insect repellant (observed at 0.5% strain, 23 °C, 3 days). In further aspects, the disclosed compositions achieve at least 95%, or at least 98%, tensile yield strength oyretention in sunscreen, insect repellant, and / or sebum. In further aspects the disclosed compositions achieve at least 75%, or at least 77%, retention of tensile elongationat break (Ebr) in sebum and at least 90% retention of tensile elongation at break (Ebr) in sunscreen and insect repellant.

[0086] As provided herein, compositions of the present disclosure are colorable. Colorable may describe the ease of coloring of the polycarbonate composition. That is, the polycarbonate composition may be sufficiently “light” in color to accept dyes, pigments, or other color treatments / additives that impart a desired hue to the composition. Conventional materials including post-consumer recycled polymers are often dark in color. Values of the present disclosure have certain values for certain color or colorimetric coordinates L*, a*, b*. The “L* value” describes the lightness-darkness property. If the L* value is 0, the object is black. If the L* value is 100 the object is white. The L* value is always positive. Compositions having an L* value further away from the extremes (0 and 100) have a more natural color, which may be the selected color for a specific application or which may enable the composition to be more easily colored. Having values further away from 0 and closer to 100 for L* results in a composition that has a much wider “color space.” The “color space” is the range of L* that can be achieved using an optional colorant, pigment and / or dye. L* may be measured using ASTM D2244 With 10 degree observer; International Commission on Illumination (CIE) Standard Illuminant D65 illuminant; specular component included (SCI) reflectance; and large aperture). The disclosed composition may exhibit an L* color value of at least 70, or at least 75, or at least 80, or at least 85, or at least 90, when measured using a spectrophotometer with D65 illumination in a 10° observer in reflection mode.

[0087] These compositions are thus suitable candidates for consumer electronics and allow for flame performance and environmental stress-cracking chemical resistance for products with customized color.

[0088] The advantageous characteristics of the compositions disclosed herein make them appropriate for an array of uses. In various aspects, the present disclosure provides compositions for use in consumer electronics.

[0089] Various combinations of elements of this disclosure are encompassed by this disclosure, for example, combinations of elements from dependent claims that depend upon the same independent claim.Definitions

[0090] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” can include the aspects “consisting of’ and “consisting essentially of.” Unless defined otherwise, all technical and scientific termsused herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0091] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a thermoplastic polymer component” includes mixtures of two or more thermoplastic polymer components. As used herein, the term “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0092] Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range includes in some aspects one or both of the first value and the second value. Similarly, when values are expressed as approximations, by use of the antecedent ‘about,’ it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0093] As used herein, the terms “about” and “at or about” mean that the amount or value in question can be the designated value, approximately the designated value, or about the same as the designated value. It is generally understood, as used herein, that it is the nominal value indicated ±10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0094] As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includesinstances where said event or circumstance occurs and instances where it does not. For example, the phrase “optional additional processes” means that the additional processes can or cannot be included and that the description includes methods that both include and that do not include the additional processes.

[0095] Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered 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 the disclosure. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the disclosure.

[0096] References in the specification and concluding aspects to parts by weight of a particular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0097] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0098] The terms “residues” and “structural units,” used in reference to the constituents of the polymers, are synonymous throughout the specification.

[0099] As used herein the terms “weight percent,” “wt. %,” and “wt%,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. 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 wt% values for all components in a disclosed composition or formulation is 100.

[0100] Unless otherwise stated to the contrary herein, all test standards are the most recent standard in effect at the time of filing this application.

[0101] As used herein, the terms “number average molecular weight” or “Mn” can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Mncan be determined for polymers, for example, polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g., polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0102] As used herein, the terms “weight average molecular weight” or “Mw” can be used interchangeably, and are defined by the formula:where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Compared to Mn, Mwtakes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the Mw. Mw can be determined for polymers, for example, polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, for example, polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0103] As used herein, degree of polymerization, n, may describe the number of monomeric units (or repeating units) in a given polymer molecule.

[0104] References in the specification and concluding claims to parts by weight of aparticular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0105] In one aspect, “substantially free” means less than 1 weight percent (wt%). In other aspects, substantially free means less than 0.9 wt%, or less than 0.8 wt%, or less than 0.7 wt%, or less than 0.6 wt%, or less than 0.5 wt%, or less than 0.4 wt%, or less than 0.3 wt%, or less than 0.2 wt%, or less than 0.1 wt%, or less than 0.05 wt%, or less than 0.01 wt%, or less than 0.001 wt%, or less than 1200 ppm, or less than 1000 ppm, or less than 800 ppm, or less than 500 ppm, or less than 200 ppm, or less than 100 ppm. In yet another aspect, substantially free can refer to an amount, if present at all, below a detectable level. In one aspect, the polycarbonate compositions and / or flame retardant additives of the present disclosure are free of or substantially free of halogen.

[0106] Each of the materials disclosed herein are either commercially available and / or the methods for the production thereof are known to those of skill in the art.

[0107] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.Aspects of the Disclosure

[0108] In various aspects, the present disclosure pertains to and includes at least the following aspects.

[0109] Aspect 1. A polycarbonate composition comprising: a. from 20 wt% to 93 wt% of a polycarbonate component comprising one or more of a virgin polycarbonate homopolymer and a post-consumer recycled polycarbonate; b. from 1 wt% to 25 wt% of a polycarbonate-polysiloxane copolymer having (1) a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and (2) a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; andc. from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive, wherein the flame retardant additive is free of or substantially free of halogen, wherein a molded sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

[0110] Aspect 2. The polycarbonate composition of Aspect 1, wherein the polycarbonate component comprises at least two different polycarbonate homopolymers.

[0111] Aspect 3. The polycarbonate composition of any one of Aspects 1-2, wherein the polycarbonate component comprises a polycarbonate homopolymer having a weight average molecular weight of 20,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

[0112] Aspect 4. The polycarbonate composition of any one of Aspects 1-3, wherein the polycarbonate component comprises a mixture of post-consumer recycled polycarbonate from multiple sources.

[0113] Aspect 5. The polycarbonate composition of any one of Aspects 1-4, wherein the phosphorous based flame retardant comprises bisphenol A diphenyl phosphate (BPADP), phenoxycyclophosphazene (PPZ), or a combination thereof.

[0114] Aspect 6. The polycarbonate composition of any one of Aspects 1-5, further comprising an additional polycarbonate-polysiloxane copolymer having a siloxane content of from 0.5 wt% to 30 wt% in an amount effective to provide the composition with a total siloxane content of 1 wt% to 25 wt%.

[0115] Aspect 7. The polycarbonate composition of any one of Aspects 1-6, wherein the polycarbonate homopolymer comprises: a first polycarbonate homopolymer having a weight average molecular weight of 19,000 to 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a second polycarbonate homopolymer having a weight average molecular weight of 29,000 to 32,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.

[0116] Aspect 8. The polycarbonate composition of any one of Aspects 1-7, wherein a molded sample of the composition exhibits improved environmental stress-cracking chemical resistance, as tested in accordance with ASTM D543, as compared to a reference compositionthat includes (1) a fluoropolymer or (2) that includes a polycarbonate-polysiloxane copolymer that has a siloxane content of less than 30 wt% or greater than 70 wt%.

[0117] Aspect 9. The polycarbonate composition of any one of Aspects 1-8, wherein the composition has a melt volume rate (MVR) of at least 10 cubic centimeters / 10 minutes (cm3 / 10 min) as tested in accordance with ASTM D1238 at 260 °C with a 2. 16 kilogram (kg) load for 360 seconds (s).

[0118] Aspect 10. The polycarbonate composition of any one of Aspects 1-9, wherein the calculated added bromine and added chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less.

[0119] Aspect 11. The polycarbonate composition of any one of Aspects 1-10, wherein the composition further comprises an anti -drip agent.

[0120] Aspect 12. The polycarbonate composition of Aspect 11, wherein the anti-drip agent comprises an encapsulated fluoropolymer.

[0121] Aspect 13. The polycarbonate composition of any one of Aspects 1-12, wherein the polycarbonate composition further comprises at least one additional additive, wherein the at least one additional additive comprises an acid scavenger, antioxidant, antistatic agent, chain extender, colorant, de-molding agent, flow promoter, lubricant, mold release agent, plasticizer, quenching agent, flame retardant, ultraviolet (UV) reflecting additive, or a combination thereof.

[0122] Aspect 14. The polycarbonate composition of any one of Aspects 1-13, wherein the polycarbonate composition exhibits an L* color value of at least 75 when tested in accordance with ASTM D2244.

[0123] Aspect 15. An article comprising the polycarbonate composition of any of Aspects 1 to 14.EXAMPLES

[0124] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and / or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensureaccuracy with respect to numbers (for example, amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. Unless indicated otherwise, percentages referring to composition are in terms of wt%.

[0125] There are numerous variations and combinations of mixing conditions, for example, component concentrations, extruder design, feed rates, screw speeds, temperatures, pressures and other mixing ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.

[0126] Various compositions were prepared by compounding on a 25 mm twin screw extruder from the raw materials shown in Table 1 (FIG. 1). All materials were blended together and fed by the main feeder. Strands including the composition were cut into pellets and dried for further molding and evaluation. All testing was conducted on pellets and molded parts. Compounding was performed on a Coperion W&P ZSK26Mc instrument, and the profdes are shown in Table 2.Table 2. Temperature profiles for compounding

[0127] Injection molding conditions are shown in Table 3. Injection molding was performed on Van Dorn machine with 85-ton clamping pressure with ASTM-family tool. Table 3. Specimen injection molding profile.

[0128] Formulations were prepared as shown in Table 4 (FIG. 2). The samples were evaluated for the following properties shown in Table 5. (FIG. 3)

[0129] Flammability tests were performed following the procedure of Underwriter’s Uaboratory Bulletin 94 entitled “Tests for Flammability of Plastic Materials, UU94,” which is incorporated herein by reference. According to this procedure, the materials were classifiedaccording to the criteria provided herein. A V-0 vertical bum was achieved where burning stopped within 10 seconds after two applications of ten seconds each of a flame to a test bar. No flaming drips were allowed. Criteria conditions for V-0 are also summarized in Table 6 (FIG. 4). Environmental stress-cracking chemical resistance (ESCR) was determined in accordance with the standards presented in Table 5 above. The criteria for environmental stress-cracking chemical resistance are provided in Table 7 (FIG. 5).

[0130] The observed properties are presented in Table 8. Thermoplastic compositions with significantly improved environmental stress cracking resistance, better impact strength, and PFAS-free flame retardance, together with good processability and color-ability were prepared and observed. PC copolymer, PC homopolymer, PCR PC, and BPADP with various loadings have been included in this disclosure. The described formulations exhibited balanced properties of melt characteristics, improved environmental stress cracking resistance, and impact resistance, while maintaining flame resistance and good colorability.

[0131] The prepared PC-polysiloxane copolymer compositions showed improved environmental stress-cracking chemical resistance compared with standard PC or standard PC / ABS formulations. These samples exhibited combined improved flame retardance (as well as PFAS free flame retardance) and environmental stress-cracking chemical resistance with good processability and colorability.

[0132] The above description is intended to be illustrative, and not restrictive. For example, the above-described examples (or one or more aspects thereof) may be used in combination with each other. Other aspects can be used, such as by one of ordinary skill in the art upon reviewing the above description. The Abstract is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Also, in the above Detailed Description, various features may be grouped together to streamline the disclosure. This should not be interpreted as intending that an unclaimed disclosed feature is essential to any claim. Rather, inventive subject matter may lie in less than all features of a particular disclosed aspect. Thus, the following claims are hereby incorporated into the Detailed Description as examples or aspects, with each claim standing on its own as a separate aspect, and it is contemplated that such aspects can be combined with each other in various combinations or permutations. The scope of the disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

[0133] It will be apparent to those skilled in the art that various modifications andvariations can be made in the present disclosure without departing from the scope or spirit of the disclosure. Other aspects of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.

[0134] The patentable scope of the disclosure is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

Claims

CLAIMSWhat is claimed is:

1. A polycarbonate composition comprising: a. from 20 wt% to 93 wt% of a polycarbonate component comprising one or more of a virgin polycarbonate homopolymer and a post-consumer recycled polycarbonate; b. from 1 wt% to 25 wt% of a polycarbonate-polysiloxane copolymer having (1) a siloxane content of from about 30 wt% to 70 wt% present in an amount effective to provide the composition with a total siloxane content of 0.5 wt% to 25 wt%, and (2) a weight average molecular weight of 26,000 to 50,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; and c. from greater than 6 wt% to 20 wt% of at least one phosphorous flame retardant additive, wherein the flame retardant additive is free of or substantially free of halogen, wherein a molded sample of the polycarbonate composition exhibits a UL-94 rating of V-0 at a thickness of 1.5 millimeters or less.

2. The polycarbonate composition of claim 1, wherein the polycarbonate component comprises at least two different polycarbonate homopolymers.

3. The polycarbonate composition of any one of claims 1-2, wherein the polycarbonate component comprises a polycarbonate homopolymer having a weight average molecular weight of 20,000 grams per mole or more, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate.

4. The polycarbonate composition of any one of claims 1-3, wherein the polycarbonate component comprises a mixture of post-consumer recycled polycarbonate from multiple sources.

5. The polycarbonate composition of any one of claims 1-4, wherein the phosphorous based flame retardant comprises bisphenol A diphenyl phosphate (BPADP), phenoxycyclophosphazene (PPZ), or a combination thereof.

6. The polycarbonate composition of any one of claims 1-5, further comprising an additional polycarbonate-polysiloxane copolymer having a siloxane content of from 0.5 wt% to 30 wt% in an amount effective to provide the composition with a total siloxane content of 1 wt% to 25 wt%.

7. The polycarbonate composition of any one of claims 1-6, wherein the polycarbonate homopolymer comprises: a first polycarbonate homopolymer having a weight average molecular weight of 19,000 to 25,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; a second polycarbonate homopolymer having a weight average molecular weight of 29,000 to 32,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or a combination thereof.

8. The polycarbonate composition of any one of claims 1-7, wherein a molded sample of the composition exhibits improved environmental stress-cracking chemical resistance, as tested in accordance with ASTM D543, as compared to a reference composition that includes (1) a fluoropolymer or (2) that includes a polycarbonate-polysiloxane copolymer that has a siloxane content of less than 30 wt% or greater than 70 wt%.

9. The polycarbonate composition of any one of claims 1-8, wherein the composition has a melt volume rate (MVR) of at least 10 cubic centimeters / 10 minutes (cm3 / 10 min) as tested in accordance with ASTM DI 238 at 260 °C with a 2. 16 kilogram (kg) load for 360 seconds (s).

10. The polycarbonate composition of any one of claims 1-9, wherein the calculated added bromine and added chlorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less; or the calculated added bromine, added chlorine, and added fluorine content of the polycarbonate composition are each about 900 ppm or less and the calculated total added bromine, added chlorine, and added fluorine content of the polycarbonate composition is about 1500 ppm or less.

11. The polycarbonate composition of any one of claims 1-10, wherein the composition further comprises an anti-drip agent.

12. The polycarbonate composition of claim 11, wherein the anti -drip agent comprises an encapsulated fluoropolymer.

13. The polycarbonate composition of any one of claims 1-12, wherein the polycarbonate composition further comprises at least one additional additive, wherein the at least one additional additive comprises an acid scavenger, antioxidant, antistatic agent, chain extender, colorant, de-molding agent, flow promoter, lubricant, mold release agent, plasticizer, quenching agent, flame retardant, ultraviolet (UV) reflecting additive, or a combination thereof.

14. The polycarbonate composition of any one of claims 1-13, wherein the polycarbonate composition exhibits an L* color value of at least 75 when tested in accordance with ASTM D2244.

15. An article comprising the polycarbonate composition of any of claims 1 to 14.

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