Modified brominated polystyrene as a compatible flame retardant for polymer compositions.

Abstract

In one aspect, the present disclosure relates to a flame-retardant composition comprising brominated polystyrene reacted with a first portion of a second polymer, and optionally at least a second portion of the second polymer that is not premixed separately with the brominated polystyrene. In some aspects, the first and second portions of the second polymer can be selected from polyamides, polyolefins, polyesters, styrenic polymers or copolymers, or any combination thereof. In any of these aspects, the flame-retardant composition of the present disclosure is well-mixed, has excellent properties, and can optionally include crosslinking to add mechanical strength. Methods for making these compositions and articles comprising these compositions are also disclosed herein.

Description

[Background technology]

[0001] Various commercial polymers, ranging from commodity to engineering plastics such as polyolefins, polystyrene, polyesters, and polyamides, are widely used in many applications due to their versatile properties. However, insufficient flame resistance can prevent their use in some applications. This is because the covalently bonded hydrocarbon backbone decomposes and burns when the polymer is exposed to fire. There are various types of flame-retardant materials that can impart fire-resistant properties to polymers. Among the many types of flame retardants, halogen compounds are widely applied to polyolefins due to their advantages, such as cost-effectiveness, good processability, and efficient flame retardancy. Brominated flame retardants (BrFRs) are primarily effective due to the acceptable range of bond energies between aliphatic or aromatic carbons and bromine. Because the bond energy is neither too high nor too low, they decompose and act as a neutralizer to hydrogen or hydroxyl radicals generated by fire.

[0002] Among the different types of BrFRs, brominated polystyrene (BPS) is a polymeric BrFR with excellent characteristics such as excellent thermal stability. However, BPS causes a decrease in mechanical properties such as tensile strength, flexural strength, and impact strength in polyolefins into which it is incorporated. The fracture toughness (critical energy release rate, G) of polypropylene containing BrFRs is low. Ic ) shows a significant reduction of up to 50% compared to neat polypropylene under impact conditions.

[0003] Despite advances in flame-retardant material research, there remains a lack of compositions that include both brominated polystyrene as a flame retardant and a polymer typically considered incompatible with brominated polystyrene, where the composition is well mixed and has excellent mechanical properties. Such compositions would be particularly useful as coatings for cable and wire components and other articles. These and other needs are met by the present disclosure. Summary of the Invention

[0004] In accordance with the objective(s) of the present disclosure, as embodied and broadly described herein, the present disclosure, in one aspect, relates to a flame-retardant composition comprising brominated polystyrene reacted in the presence of a first portion of a second monomer or second polymer, and optionally at least a second portion of the second polymer that is unreacted with the brominated polystyrene. In some aspects, the first and second portions of the second polymer can be selected from polyamides, polyolefins, polyesters, styrenic polymers or copolymers, or any combination thereof. In any of these aspects, the flame-retardant compositions of the present disclosure are well-mixed, have excellent properties, and can optionally include crosslinking to add mechanical strength. Methods for making these compositions and articles comprising these compositions are also disclosed herein.

[0005] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one of ordinary skill in the art upon examination of the following drawings and detailed description. All such additional systems, methods, features, and advantages are intended to be included within this description, be within the scope of the disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments can be used in all aspects of the present disclosure taught herein. Furthermore, the individual features of the dependent claims, and all optional and preferred features and modifications of the described embodiments, are combinable and interchangeable with each other. [Brief explanation of the drawings]

[0006] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals indicate corresponding parts throughout the several views.

[0007] [Figure 1]1 shows the H NMR spectroscopy used to calculate the Mn ratio in XLPE / gBPS-0.4 wt% polymer blends. [Figure 2] 1 shows the 1H NMR spectroscopy used to calculate the Mn ratio in the XLPE / gBPS-2.1 wt% polymer blend. [Figure 3] 1 is a schematic diagram showing that inventive mixtures of brominated polystyrene and polyolefin resins do not mix well (left panel), but that modified brominated polystyrene blends well with polyolefins and other resins. [Figure 4A] FIG. 4B is a schematic diagram showing one potentially modified form of brominated polystyrene to include reactive groups such as trimethoxysilyl groups, while FIG. 4B is a schematic diagram of commercially available resins that can include, but are not limited to, polyolefins that have also been modified to include reactive groups such as trimethoxysilyl groups. [Figure 5] 4A and 4B are schematic diagrams illustrating cross-linking of reactive groups on brominated polystyrene (see FIG. 4A) and a commercial resin (see FIG. 4B) according to one embodiment of the flame retardant composition described herein.

[0008] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure provides flame-retardant compositions, methods for making the flame-retardant compositions, and articles incorporating the flame-retardant compositions. The present disclosure is advantageous because it uses flame retardants that do not bioaccumulate and do not contribute to human or animal health problems. This can be particularly important because the flame-retardant compositions can be used as jackets for cables and wires that may be exposed to the environment. The flame-retardant compositions have a homogeneous composition that allows for the production of molded parts and articles with improved mechanical properties compared to materials currently used in cable or wire applications. The flame-retardant compositions can also have improved appearance, including improved gloss.

[0010] Disclosed herein is a flame-retardant composition comprising a brominated polystyrene modified via a first portion of a second polymer. In some embodiments, the composition further comprises at least a second portion of the second polymer that does not react in the presence of the brominated polystyrene. In one embodiment, the first and second portions of the second polymer comprise a polyamide, a polyolefin, a polyester, a styrenic polymer or copolymer, or any combination thereof.

[0011] In one embodiment, when the first and second portions of the second polymer comprise a polyamide, the polyamide is or comprises nylon 6,6, nylon 6, nylon 6,10, nylon 11, nylon 6,12, nylon 12, nylon 6,9, nylon 4,6, poly(m-phenylene isophthalamide), poly(p-phenylene terephthalamide), copoly(p-phenylene / d,4'-diphenyl ether terephthalamide), PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-xylene sebacamide), poly(m-xylene adipamide), copolymers thereof, or any combination thereof. In an embodiment, when the first and second portions of the second polymer comprise a polyolefin, the polyolefin is or comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), very low density polyethylene (ULDPE), medium density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), ethylene-octene copolymer, stereoblock PP, olefin block copolymer, propylene-butane copolymer, polyisobutylene (PIB), poly(α-olefin), ethylene propylene rubber (EPR), ethylene propylene diene monomer rubber (EPDM rubber), high density polyethylene (HDPE), ultra high density polyethylene (UHDPE), cross-linked polyethylene (PEX or XLPE), or any combination thereof. In yet another embodiment, when the first and second portions of the second polymer comprise a polyester, the polyester is or comprises polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly(cyclohexylene dimethylene terephthalate) (PCT), polylactic acid (PLA), polycaprolactone (PCL), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), or any combination thereof. In yet another embodiment, when the first and second portions of the second polymer comprise a styrenic polymer or copolymer, the styrenic polymer or copolymer is or comprises poly(styrene-co-acrylonitrile) (SAN), poly(acrylonitrile-co-butadiene-styrene) (ABS), or any combination thereof.

[0012] In another embodiment, the brominated polystyrene comprises a plurality of monomer units having the structure of Formula I: [ka] In the formula, x in each of the plurality of monomer units is independently 0 to 4; R1 in each of the plurality of monomer units is independently hydrogen, bromine, NR 1a R 1b or a pendant group containing at least two carbons; R 1a and R 1b are independently selected from C1 to C30 straight or branched chain hydrocarbons, and R2 in each monomer unit of the plurality of monomer units is independently selected from hydrogen or a pendant group containing at least two carbons.

[0013] Further in this aspect, the pendant group attached to R1 and / or R2 can comprise at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbons, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0014] Also disclosed herein are flame retardant compositions in which each R1 is hydrogen or bromine and each R2 is independently hydrogen or a pendant group containing at least two carbons. In another embodiment, each R2 is hydrogen and each R1 is independently hydrogen, bromine, or a pendant group containing at least two carbons.

[0015] In one embodiment, the average value of x across multiple monomer units is from about 2 to about 5, or from about 2 to about 4, or from about 2 to about 3, or about 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, or about 5, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. Further, in this embodiment, x can be an integer or can be a decimal or fractional value rather than an integer.

[0016] In one embodiment, about one pendant group containing at least two carbons is present at R1 or R2 at a level of 0 to 250 of the total monomer units. In the brominated polystyrene of Formula I, there can be a pendant group on 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or about 250 of the monomer units, or any combination of the foregoing values, or a range encompassing any of the foregoing values.

[0017] In another embodiment, the flame retardant composition of the present disclosure comprises about 0 to about 2.1 wt. % pendant groups, about 0 to 0.75 wt. %, about 0.5 to 0.7 wt. %, about 1 to 2 wt. %, or about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, or about 2.1 wt. % pendant groups, per total weight of the brominated polystyrene, or any combination of the aforesaid values, or a range encompassing any of the aforesaid values.

[0018] In some embodiments, the pendant group having at least two carbons of at least one of the plurality of monomer units comprises a trimethoxysilyl group. [ka] Or any combination thereof can be selected.

[0019] In one embodiment, the first portion of the second polymer includes at least one pendant group comprising a trimethoxysilyl group. In yet another embodiment, the flame retardant composition includes at least one crosslink between a trimethoxysilyl group on the brominated polystyrene and a trimethoxysilyl group in the first portion of the second polymer.

[0020] In certain embodiments, either R1 or R2 pendant groups of Formula I above may be introduced into the brominated polystyrene during the modification reaction.

[0021] In certain embodiments, at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 Acrylate or vinyl monomers having pendant groups containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbons, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values, may be polymerized during the modification reaction to form oligomers or homopolymers having at least two repeat units.

[0022] In some embodiments, these acrylate or vinyl oligomers or homopolymers have from 2 to 1000 repeat units, including any total number of repeat units within this range. The oligomers and homopolymers present may all have a different number of repeat units, the same number of repeat units, or any distribution of repeat units within this range.

[0023] In some embodiments, the flame retardant compositions disclosed herein can also include a synergist. In further embodiments, the synergist can be antimony trioxide (herein, Sb2O3 or ATO) or another synergist. In other embodiments, the flame retardant composition can include about 1 wt. % to about 10 wt. %, about 1 wt. % to about 5 wt. %, about 5 wt. % to about 10 wt. %, or about 3 wt. % to about 7 wt. % of Sb2O3 or other synergist, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt. % of Sb2O3 or other synergist, any combination of the foregoing values, or a range encompassing any of the foregoing values.

[0024] In some embodiments, the compositions of the present disclosure also include a filler, such as, for example, talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH), AlO(OH), Mg(OH), kaolinite, wollastonite, mica, glass beads, or any combination thereof. In one embodiment, the compositions of the present disclosure also include a reinforcing agent, such as, for example, glass fiber.

[0025] In one embodiment, an article comprising the flame-retardant composition of the present disclosure is disclosed herein. In one embodiment, the article has a flammability rating of V0 according to test method UL94. In one embodiment, the article can include molded parts for use in various automotive applications, such as housings, connectors for electronic devices, and / or circuit boards, components within the engine compartment, seats, insulation, and interior components, as well as residential applications, including insulation, carpeting, and wall coverings. In another embodiment, the article can be a jacket for cables and / or wires. In yet another embodiment, the article of the present disclosure can be or include a textile and / or adhesive.

[0026] The present disclosure provides a method of making a flame-retardant composition. In one aspect, the method includes mixing an acrylate monomer with brominated polystyrene to form a precursor mixture. The mixing step can be carried out for about 0.1 minutes to about 30 minutes, or about 0.1 to about 5 minutes, or about 5 minutes to about 15 minutes, or about 15 minutes to about 30 minutes, or for a period of about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes, or any combination of the foregoing values, or a range encompassing any of the foregoing values. The mixing step can be carried out at a temperature of about 160°C to about 230°C, about 160°C to about 180°C, about 175 to about 200°C, about 200 to about 230°C, or about 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, or about 230°C, or any combination of the foregoing values, or a range encompassing any of the foregoing values.

[0027] The precursor mixture is blended to produce a brominated polystyrene modified by the presence of the first portion of the second polymer. The blending step can be carried out for about 0.1 minutes to about 30 minutes, or about 0.1 to about 5 minutes, or about 5 minutes to about 15 minutes, or about 15 minutes to about 30 minutes, or for a period of about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes. The blending step can be carried out at a temperature of about 160°C to about 230°C, about 160°C to about 180°C, about 175 to about 200°C, about 200 to about 230°C, or about 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, or about 230°C, or any combination of the foregoing values, or any range including any of the foregoing values.

[0028] The brominated polystyrene containing a first portion of a second polymer can then be mixed with a second portion of a second polymer. This mixing step can be carried out for a period of about 0.1 minutes to about 30 minutes, or about 0.1 to about 5 minutes, about 5 minutes to about 15 minutes, or about 15 minutes to about 30 minutes, or for a period of about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes, or any combination or range of the foregoing values. This mixing step can be carried out at a temperature of about 160°C to about 230°C, about 160°C to about 180°C, about 175 to about 200°C, about 200 to about 230°C, or about 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, or about 230°C, or any combination of the foregoing values, or a range including any of the foregoing values. For example, a synergist, such as antimony trioxide, can be added during any part of the mixing process.

[0029] The method can also optionally include curing the flame-retardant composition in water. Curing can be carried out for a period of about 1 hour to about 10 days, or about 1 hour to about 24 hours, or about 1 day to about 5 days, or about 5 days to about 10 days, or for about 1, 2, 6, 12, 18, or 24 hours, or about 2, 3, 4, 5, 6, 7, 8, 9, or about 10 days, or any combination of, or ranges encompassing, any of the foregoing values. In another embodiment, curing can be carried out at a temperature of about 25°C to about 200°C, about 25°C to about 50°C, about 50°C to about 75°C, or about 75°C to about 100°C, or about 25, 50, 100, 150, or about 200°C, or any combination of, or ranges encompassing, any of the foregoing values.

[0030] In one embodiment, the acrylate monomer can have at least 5 carbon atoms. For example, the acrylate monomer can be or include 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), vinyltrimethoxysilane, vinyltriethoxysilane, or other vinyl-containing species, or combinations thereof, used by those skilled in the art of moisture-cured wire and cable manufacturing. In some embodiments, the precursor mixture further includes an initiator, such as, for example, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, cumyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, azobisisobutyronitrile, or any combination thereof.

[0031] In certain embodiments, brominated polystyrene may be modified to contain reactive groups by reactive extrusion according to the procedure shown in Scheme 1A or Scheme 1B. A schematic of this process is shown in Figure 4A. [ka]

[0032] In certain embodiments, a resin, such as, for example, a polyolefin resin, may be modified to contain reactive groups by reactive extrusion according to the procedure shown in Scheme 2. A schematic of this process is shown in Figure 4B. [ka]

[0033] In certain embodiments, the grafted brominated polystyrene and resin can be crosslinked by water curing or another method according to the procedure shown in Scheme 3. A schematic of this process is shown in FIG. [ka]

[0034] Schemes 4-7 illustrate some of the many modifications and other embodiments of the disclosed compositions and methods that will occur to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing description and the associated drawings. Accordingly, it is to be understood that the disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Those skilled in the art will recognize many variations and adaptations of the embodiments described herein. These variations and adaptations are within the teachings of the present disclosure and are intended to be encompassed by the scope of the claims herein. [ka] [ka]

[0035] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0036] As will be apparent to those skilled in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has distinct components and features that may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0037] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect described herein be construed as requiring that its steps be performed in a particular order. Thus, where a method claim does not specifically recite in the claim or description that the steps are to be limited to a particular order, no order is intended to be inferred in any respect. This applies to any possible non-expressive basis for interpretation, including matters of logic regarding the arrangement of steps or operational flow, apparent meaning derived from grammatical organization or punctuation, or the number or type of aspects described herein.

[0038] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is intended to entitle the present invention to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein may be different from the actual publication dates, which may require independent confirmation.

[0039] Although aspects of the present disclosure may be described and claimed in particular statutory classes, such as a systems statutory class, this is for convenience only, and those skilled in the art will understand that each aspect of the present disclosure may be described and claimed in any statutory class.

[0040] It should also be understood that the terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the disclosed compositions and methods belong. Terms, such as those defined in commonly used dictionaries, should be interpreted to have a meaning consistent with their meaning in the context of the present specification and related technical fields, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0041] Prior to describing the various aspects of this disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in this disclosure.

[0042] definition As used herein, "comprising" should be interpreted as specifying the presence of the stated features, components, steps, or parts as referred to, but does not exclude the presence or addition of one or more features, components, steps, or parts, or groups thereof. Furthermore, each of the terms "by," "comprising," "comprises," "comprised of," "including," "includes," "included," "involving," "involves," "involved," and "such as" are all used in an open, non-limiting sense and can be used interchangeably. Furthermore, the term "comprising" is intended to include examples and aspects encompassed by the terms "consisting essentially of" and "consisting of." Similarly, the term "consisting essentially of" is intended to include examples encompassed by the term "consisting of."

[0043] As used in this 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 "monomer," a "polyamide," or a "filler" includes, but is not limited to, mixtures or combinations of two or more such monomers, polyamides, or fillers, etc.

[0044] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in the form of a range. It will further be understood that the endpoints of each range are significant both in relation to the other endpoint and independently of the other endpoint. It is also understood that there are several values ​​disclosed herein, and that each value, in addition to the value itself, is herein disclosed as "about" that particular value. For example, if the value "10" is disclosed, then "about 10" is also disclosed. Ranges can be expressed herein as from "about" one particular value and / or to "about" another particular value. Similarly, when values ​​are expressed as approximations by the use of the preceding "about," it will be understood that the particular value forms a further aspect. For example, if the value "about 10" is disclosed, then "10" is also disclosed.

[0045] When a range is expressed, a further embodiment includes from the one particular value and / or to the other particular value. For example, if the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure; for example, the phrase "from x to y" includes ranges from "x" to "y," as well as ranges greater than "x" and less than "y." Ranges can also be expressed as upper limits, e.g., "about x, y, z, or less," and should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "less than x," "less than y," and "less than z." Similarly, the phrase "about x, y, z, or more" should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "greater than x," "greater than y," and "greater than z." Additionally, the phrase "about 'x' to 'y'" (where 'x' and 'y' are numerical values) includes "about 'x' to about 'y'."

[0046] It should be understood that such range formats are used for convenience and brevity and, therefore, should be interpreted flexibly to include not only the numerical values ​​expressly recited as range limits, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were expressly recited. To illustrate, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values ​​of about 0.1% to about 5%, but also individual values ​​(e.g., about 1%, about 2%, about 3%, and about 4%) and subranges (e.g., about 0.5% to about 1.1%, about 5% to about 2.4%, about 0.5% to about 3.2%, and about 0.5% to about 4.4%, as well as other possible subranges) within the indicated range.

[0047] As used herein, the terms "about," "approximate," "about," and "substantially" mean that the quantity or value in question may be an exact value or value that will provide the equivalent result or effect as recited in the claims or taught herein. That is, it is understood to mean that the amount, size, formulation, parameter, and other quantities and features are not and need not be exact, but may be approximate and / or larger or smaller, as necessary, to reflect tolerances, conversion factors, rounding, measurement error, and the like, and other factors known to those skilled in the art, so long as the equivalent result or effect is achieved. In some circumstances, a value that will provide the equivalent result or effect cannot be reasonably determined. In such cases, as used herein, "about" and "at or about" are generally understood to mean the nominal value, subject to a ±10% variation, unless otherwise indicated or inferred. In general, a quantity, size, formulation, parameter, or other quantity or feature is "about," "approximate," or "at or about," regardless of whether it is expressly stated as such. When "about," "approximately," or "at or about" is used before a quantitative value, it is understood that the parameter also includes the particular quantitative value itself, unless otherwise specified.

[0048] As used herein, the term "effective amount" refers to an amount sufficient to achieve the desired physical property modification of a composition or material. For example, an "effective amount" of brominated polystyrene refers to an amount sufficient to achieve the desired improvement in the properties controlled by the formulation components, such as achieving a desired level of flame retardancy while maintaining good mechanical properties. The specific level required as an effective amount in terms of weight percent in the composition depends on various factors, including the amount and type of polymer, the amount and type of brominated polystyrene, including the degree of bromine atom substitution, the amount and type of any filler used, and the end use of the article made using the composition.

[0049] As used herein, the term "any" or "optionally" means that a subsequently described event or circumstance may or may not occur, and the description includes instances in which the event or circumstance occurs and instances in which it does not. This means:

[0050] "Test Method UL 94" refers to a test method produced by Underwriters Laboratories (UL) intended to serve as a preliminary indication of the acceptability of plastics for use as part of an article with respect to flammability. For example, to achieve a V-0 flammability rating, after two applications of a flame set on a test bar for 10 seconds each, the burning of the article ceases within 10 seconds. There may be no flaming drip.

[0051] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (ie, one atmosphere).

[0052] Having now described aspects of the present disclosure, the following examples generally illustrate some additional aspects of the present disclosure. Aspects of the present disclosure will be described in conjunction with the following examples and corresponding text and figures, but are not intended to limit the scope of the present disclosure. On the contrary, all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure are intended to be encompassed. [Example]

[0053] The following examples are presented 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 of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is °C or is ambient temperature, and pressure is at or near atmospheric.

[0054] Example 1: Preparation of XLPE / gBPS-0.4 wt% polymer blend Modification Reaction Dicumyl peroxide (DCP, 0.163 g) solid was dissolved in 0.326 g of 3-(trimethoxylsilyl)propyl methacrylate (TMSPMA). This TMSPMA / DCP solution was then manually mixed with 6.20 g of BPS powder. The mixture was then extruded in a twin-screw extruder (ThermoFisher Scientific HAAKE MiniCTW). The mixture was added to a Micro-Conical Twin Screw Compounder and blended for 10 minutes at 185°C. The screw speed was 300 rpm. The modified product rBPS (reactive BPS) was produced in an amount of 6.21 g.

[0055] Polymer Ratio Calculation The modified product rBPS (0.5 g) was dissolved in 5 mL of THF (tetrahydrofuran) via ultrasonication. Then, this solution was added dropwise to 50 mL of methanol solvent with stirring. rBPS precipitated. The solution was filtered, and the rBPS precipitate was collected. This purification process was repeated two more times to remove residual unreacted TMSPMA monomer and DCP decomposition products. The rBPS precipitate was dried overnight in a vacuum oven at 120 °C. The polymer ratio of rBPS was determined by proton nuclear magnetic resonance (NMR) analysis. 1 100 mg of purified rBPS was dissolved in 1 mL of deuterated chloroform (CDCl3), and the solution was 1 The 1H NMR peak was used for the calculation. BPS had a bromine content of 68.5% by weight, which meant that in each repeating unit of the BPS chemical structure, 2.75 Br atoms and 2.25 H atoms were present connected to the benzene ring of BPS. The molar mass of the repeating unit of BPS was 321 g / mol, and the molar mass of TMSPMA was 248 g / mol. The proton atom in the trimethoxy group of TMSPMA was selected as the characteristic peak for the calculation. 1 The H NMR results are shown in Figure 1, and the calculation procedures were as follows.

[0056] For every nine proton atoms in the trimethoxy group (chemical shift δ = 3.60), there are 445.8 proton atoms connecting to the benzene ring of BPS (δ = 5.6-8.0). This means that if TMSPMA molecules are present in the rBPS polymer chain, there are (445.8 x 0.98) / 2.25 = 194 repeat units of BPS. Note that the factor 0.98 is applied here to account for the contribution from the peak area of ​​deuterated chloroform. Then, calculate the polymer ratio, i.e., w(TMSPMA) / w(rBPS) or w(TMSPMA) / (w(TMSPMA) + w(BPS)): 248 / (248+194×321)=0.004=0.4% by weight.

[0057] The rBPS product with a polymer ratio of 0.4 wt% is referred to as rBPS-0.4 wt%.

[0058] Preparation of XLPE / rBPS-0.4 wt% polymer blend 1 Unlike the purification process for H NMR measurements, the rBPS product obtained in step 1 was placed in a vacuum oven (10 mm Hg / 180 °C / 1 h) to remove residual TMSPMA monomer. The purified rBPS was then used in the polymer blend as follows.

[0059] Crosslinkable polyethylene (rPE) (LyondellBasell AQUATHENE 120000, 39.0 g) and 0.4 wt% rBPS (13.0 g) were first blended for 7 minutes in a twin-screw Haake mixer (Haake Buchler Rheocord System 40) at 225 °C. The blend was further blended with a catalyst masterbatch (LyondellBasell AQUATHENE CM04482, 2.6 g) at 185 °C for 7 minutes at a weight composition of rPE / rBPS / Cat. = 75 / 25 / 5. The rPE / rBPS / Cat. blend was injection molded into rectangular and tensile bars for mechanical testing using a ThermoFisher Scientific HAAKE MiniJet Pro piston injection molding system. These bars were placed in a vial filled with water and placed in a 90 °C oven overnight. The methoxysilane groups must react with each other in this water curing step, and a cross-linked sample, i.e., XLPE / rBPS-0.4 wt% polymer blend, is finally achieved.

[0060] The Izod test is 8.5 kJ / m for XLPE / BPS. 2 , and 84.8kJ / m for XLPE 2 compared to 5.88kJ / m 2 The XLPE / BPS composite showed an impact strength of 2%±1%. Hot creep testing showed an elongation of 2%±1%, which is an improvement compared to 5%±2% for XLPE / BPS and 7%±2% for XLPE. A complete description of Izod impact and hot creep testing can be found in Example 6.

[0061] Example 2: Preparation of XLPE / rBPS-2.1 wt% polymer blend rBPS-2.1 wt% was prepared according to the procedure of Example 1, except that 6.00 g of BPS, 1.50 g of TMSPMA, and 0.30 g of DCP were used. The grafting ratio was calculated according to the same calculation procedure of Example 1, as shown in Figure 2. 1 Calculated using H NMR results.

[0062] An XLPE / gBPS-2.1 wt% polymer was prepared according to Example 1 using 39.0 g of rPE, 13.0 g of rBPS-2.1 wt%, and 2.6 g of the catalyst masterbatch.

[0063] The Izod test is 8.5 kJ / m for XLPE / BPS. 2 , and 84.8kJ / m for XLPE 2 compared to 8.81kJ / m 2 In hot creep tests, the elongation was 5% ± 2%, compared to 5% ± 2% for XLPE / BPS and 7% ± 2% for XLPE. The following was shown.

[0064] Example 3. Preparation of PP / rBPS2(BPS-g-AMEH) / EBA-g-MAH polymer blends Modification Reaction Dicumyl peroxide (DCP, 0.7 g), 2-aminoethyl methacrylate hydrochloride (AMEH, 3.5 g), and 65.8 g of BPS powder were mixed by hand in a plastic bag. The mixture was charged into a twin-screw internal mixer (Haake Rheocord 40) and blended at 200 °C and 60 RPM for 10 minutes. After reactive extrusion, approximately 50 g was recovered from the internal mixer. The resulting material is a mixture of rBPS2 (reactive BPS2, BPS-g-AMEH) and poly(AMEH), as generally represented in Scheme 4.

[0065] Preparation of PP / rBPS2 / EBA-g-MAH polymer blends 43 g of polypropylene homopolymer (PP, LyondellBasell, Prfoax-6523), 5 g of modified rBPS2, and 2 g of maleic anhydride-grafted ethylene butyl arylate copolymer (EBA-g-MAH, SK Functional Polymers, Lotader 3410) were blended in a twin-screw internal mixer (Haake Rheocord 40) at 230 °C and 50 RPM for 5 minutes. The PP / rBPS2 / EBA-g-MAH blend was injection molded into Izod impact bars using a ThermoFisher Minijet Pro under injection mold pressure of 670 psi, barrel temperature: 230 °C, mold temperature: 50 °C, and cooling time: 10 seconds.

[0066] 43 g of PP (LyondellBasell, Prfoax-6523), 5 g of unmodified BPS, and 2 g of EBA- g -MAH (SK Functional Polymer, Lotader 3410) were blended and injection molded under the same conditions as described for the preparation of PP / rBPS2 / EBA- g -MAH.

[0067] Room-temperature Izod impact tests showed an impact strength of 5.9 kJ / m for PP / rBPS2 / EBA-g-MAH, a 12% improvement compared to 4.8 kJ / m for PP / BPS / EBA-g-MAH. Morphological observations of PP / BPS / EBA-g-MAH and PP / rBPS2 / EBA-g-MAH by transmission electron microscopy (JEOL-1200X) are shown in Figures 6A and 6B, respectively. The location of the elastomer (EBA-g-MAH) is clearly different between PP / BPS / EBA-g-MAH and PP / rBPS2 / EBA-g-MAH. EBA-g-MAH is dispersed separately in PP / BPS / EBA-g-MAH (Figure 6A). On the other hand, EBA-g-MAH surrounds rBPS2 in the case of PP / rBPS2 / EBA-g-MAH (Fig. 6B).

[0068] Example 4. Preparation of PPA / rBPS3 polymer blends Preparation of rBPS3 (BPS-g-GMA) Dicumyl peroxide (DCP, 22.68 g) and glycidyl methacrylate (GMA, 45.46 g) were premixed with 2199.96 g of BPS powder. The premix was fed into a Werner & Pfleider (Coperion) ZSK-30 twin-screw extruder (L / D 24, screw diameter 30 mm, barrel temperature 210-235 °C from the hopper to the die) at a screw speed of 175 RPM and a feed rate of 14 kg / h. A vacuum stack was used to remove unreacted GMA monomer. Manually cut pellets produced from the die were a mixture of modified rBPS3 (reactive BPS3, BPS-g-GMA) and poly(GMA).

[0069] 39g of PPA (Polyphthalamide, DuPont HTN-502, PA6T / 66 type) and 11 g of rBPS3 was mixed by hand in a plastic bag. The mixture was extruded in a ThermoFisher Process 11 twin-screw extruder equipped with one feeder. The barrel temperature of the extruder was 285–320°C from the hopper to the die. The twin-screw speed was 150 RPM, and the feed rate was 0.2 kg / h. The extruded strands were cooled on a conveying belt and then chopped in a pelletizer. The chopped pellets after extrusion were injection molded via a ThermoFisher Minijet Pro for Izod bars under injection pressure: 3,450 psi, barrel temperature: 345°C, mold temperature: 90°C, and cooling time: 15 seconds. A PPA / BPS polymer blend (39 g of PPA and 11 g of unmodified BPS) was extruded and injection molded in the same manner as the PPA / rBPS3 polymer blend.

[0070] Room temperature Izod impact tests showed an impact strength of 2.8 kJ / m for PPA / rBPS3, a 40% improvement compared to 2.0 kJ / m for PPA / BPS. The mean particle size and total number of dispersed BPS in PPA / rBPS3 were 0.23 μm and 45, respectively (Figures 8A and 8B), indicating better dispersion compared to the mean particle size and total number of dispersed BPS in PPA / BPS, which were 2.08 μm and 7, respectively (Figures 7A and 8B).

[0071] Example 5. Preparation of PPA / rBPS4 polymer blends Preparation of rBPS4 (BPS-g-MAH) Dicumyl peroxide (DCP, 22.68 g) and maleic anhydride (MAH, 36.29 g) were premixed with 2209.3 g BPS powder. The final material was produced using the same method as described for the preparation of rBPS3. The resulting material was a mixture of rBPS4 (reactive BPS4, BPS-g-MAH), poly(MAH), 1,2,3,4-cyclobutanetetracarboxylic dianhydride, carbon dioxide, and polyvinylene ketone anhydride, including other potential ring-opened and branched structures that could be envisioned by those skilled in the art.

[0072] 39 g of PPA and 11 g of rBPS4 were mixed by hand in a plastic bag, and the mixture was extruded and injection molded in the same manner as described for the preparation of the PPA / rBPS3 polymer blend.

[0073] Room temperature Izod impact tests showed an impact strength of 2.9 kJ / m for PPA / rBPS4, a 45% improvement compared to 2.0 kJ / m for PPA / BPS. The mean particle size and total number of dispersed BPS in PPA / rBPS4 were 0.02 μm and 271, respectively (Figures 9A and 9B), indicating better dispersion compared to the mean particle size and total number of dispersed BPS in PPA / BPS, which were 2.08 μm and 7 (Figures 7A and 8B).

[0074] Example 6. Testing Procedure Room temperature and low temperature notched Izod impact tests For room temperature Izod impact testing, injection-molded Izod bars (63.5 mm x 10.2 mm x 3.2 mm with a 10.16 mm V-notch depth) were subjected to Izod impact testing at 25°C using a 2.7 J pendulum hammer one day after their injection molding. For low-temperature Izod impact testing, fully cross-linked V-shaped rectangular bars (63.5 mm x 10.2 mm x 3.2 mm, 10.16 mm V-notch depth) were dried overnight in a vacuum oven before testing. They were pre-cooled for 1 hour in an environmental chamber at -37°C. These bars were then immediately tested / impacted with an 11.3 J pendulum hammer. The resulting energy absorption was read. Izod impact strength was calculated as follows: Izod impact strength = energy absorption / cross-sectional area.

[0075] Hot Creep Test Tensile bars (gauge width 3.0 mm x thickness 3.2 mm) were dried overnight in a vacuum oven before testing. Hot creep tests were performed in accordance with UL-44 and UL-2556 standards. Before testing, the gauge length of the tensile bar was measured and set to 1.0. The bar was preheated in an oven (150°C), and then a 196 g object was hung from it to apply a load stress of 0.2 MPa. The bar was tested under these conditions (150°C / 0.2 MPa / 15 min). After 15 min, the instantaneous length L was measured. The elongation was calculated by (L-L0) / L0. Low creep was desirable for this test.

[0076] dynamic mechanical analysis The samples (35 mm x 8 mm x 3.2 mm) were tested using a TA Instruments ARES-G2 rheometer from 30 °C to 200 °C at a ramping rate of 10 °C / min. The test frequency was 1 Hz, and a small strain of 0.1% was applied.

[0077] Particle size analysis Dispersed BPS phases were manually selected as ellipses in transmission electron microscope images taken with a JEOL JEM-1400 and processed using the "Binary Imaging" function in ImageJ software. The average particle size and total number of particles were analyzed using the "Analyze particles" function in ImageJ software.

[0078] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the present disclosure. Many variations and modifications can be made to the above-described embodiment(s) without substantially departing from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included herein within the scope of the present disclosure and protected by the following claims. References 1. Li, HM; et al, 2002, Polymer, 43:5455-5461. 2. Passaglia, E.; et al, 2004, Macromol Symp, 218:61-70. 3. Won Ho Jo, et al, 1996, Polymer, 37:1709-1714.

Claims

1. A flame retardant composition comprising a brominated polystyrene modified with a first portion of a monomer or a second polymer.

2. The flame retardant composition of claim 1 further comprising at least a second portion of the second polymer.

3. 3. The flame retardant composition of claim 1 or 2, wherein the first portion and the second portion of the second polymer comprise a polyamide, a polyolefin, a polyester, a styrenic polymer or copolymer, or any combination thereof.

4. 4. The flame retardant composition of claim 3, wherein the polyamide comprises nylon 6,6, nylon 6, nylon 6,10, nylon 11, nylon 6,12, nylon 12, nylon 6,9, nylon 4,6, poly(m-phenylene isophthalamide), poly(p-phenylene terephthalamide), copoly(p-phenylene / d,4'-diphenyl ether terephthalamide), PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-xylylene sebacamide), poly(m-xylylene adipamide), copolymers thereof, or any combination thereof.

5. 5. The flame retardant composition of claim 3, wherein the polyolefin comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), very low density polyethylene (ULDPE), medium density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), ethylene-octene copolymer, stereoblock PP, olefin block copolymer, propylene-butane copolymer, polyisobutylene (PIB), poly(α-olefin), ethylene propylene rubber (EPR), ethylene propylene diene monomer rubber (EPDM rubber), high density polyethylene (HDPE), ultra high density polyethylene (UHDPE), cross-linked polyethylene (PEX or XLPE), or any combination thereof.

6. 6. The flame retardant composition of any one of claims 3 to 5, wherein the polyester comprises polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly(cyclohexylene dimethylene terephthalate) (PCT), polylactic acid (PLA), polycaprolactone (PCL), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), or any combination thereof.

7. The styrenic polymer or copolymer poly(styrene-co-acrylonitrile) (SAN), poly(acrylonitrile-co-butadiene-styrene) (ABS), or any combination thereof, the flame retardant composition of any one of claims 3 to 6.

8. the brominated polystyrene comprises a plurality of monomer units having the structure of Formula I, 【Chemistry 1】 wherein x in each monomer unit of the plurality of monomer units is independently 0 to 4; R in each of the plurality of monomer units １ are independently hydrogen, bromine, NR １ａ R １ｂ or a pendant group containing at least two carbons; R １ａ and R １ｂ are independently selected from C1 to C30 straight or branched chain hydrocarbons; R in each of the plurality of monomer units ２ The flame retardant composition of any one of claims 1 to 7, wherein independently comprise hydrogen or a pendant group containing at least two carbons.

9. Each R １ is hydrogen or bromine, and each R ２ are independently hydrogen or the pendant group comprising at least two carbons, with the proviso that at least one pendant group is present in the first portion of the second polymer.

10. Each R ２ is hydrogen, and each R １ are independently hydrogen, bromine, or the pendant group comprising at least two carbons, with the proviso that at least one pendant group is present in the first portion of the second polymer.

11. The flame retardant composition of any one of claims 1 to 10, wherein the average value of x across the plurality of monomer units is from about 2 to about 5.

12. about one pendant group containing at least 5 carbons is present at R for every 5 to 150 monomer units of said plurality of monomer units; １ or R ２ The flame retardant composition according to any one of claims 1 to 11, wherein

13. The flame retardant composition of any one of claims 1 to 11, comprising from about 0 to about 2.1 weight percent pendant groups based on the total weight of the brominated polystyrene.

14. The flame retardant composition of any one of claims 1 to 11, comprising a homopolymer polyacrylate of a vinyl polymer containing pendant side chains polymerized in the presence of brominated polystyrene.

15. R of at least one of the plurality of monomer units １ or R ２ The flame retardant composition of any one of claims 8 to 14, wherein the pendant group containing at least two carbons in the formula (I) comprises a trimethoxysilyl group.

16. pendant groups containing at least 5 carbons, 【Chemistry 2】 The flame retardant composition according to any one of claims 13 to 15, having a structure selected from the group consisting of:

17. The flame retardant composition of any one of claims 8 to 16, wherein the first portion of the second polymer comprises at least one pendant group comprising a trimethoxysilyl group.

18. Sb ２ O ３ The flame retardant plastic composition according to any one of claims 1 to 17, further comprising:

19. The flame retardant plastic composition comprises about 1 wt % to about 10 wt % Sb ２ O ３ 20. The flame retardant plastic composition of claim 18, comprising:

20. The flame retardant composition of any one of claims 1 to 19, further comprising a filler.

21. The filler may be talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH) ３ , AlO(OH), Mg(OH) ２ 21. The flame retardant composition of claim 20, comprising: kaolinite, wollastonite, mica, glass beads, or any combination thereof.

22. The flame retardant composition of any one of claims 1 to 21, further comprising a reinforcing agent.

23. 23. The flame retardant composition of claim 22, wherein the reinforcing agent comprises glass fibers.

24. An article comprising the flame retardant composition of any one of claims 1 to 23.

25. 21. The article of claim 20, wherein the article has a flammability rating of V0 according to test method UL94.

26. 22. The article of claim 20 or 21, wherein the article comprises a cable or wire jacket, an automotive part, an electronic component, insulation, carpet, wall covering, textile, adhesive, or any combination thereof.

27. A method for making the flame retardant composition of any one of claims 2 to 23, comprising: (a) mixing an acrylate monomer containing at least two carbon atoms with brominated polystyrene to form a precursor mixture, and blending the precursor mixture to form the second polymer; forming said brominated polystyrene modified by the presence of said first portion of (b) mixing the brominated polystyrene grafted to the first portion of the second polymer with the second portion of the second polymer.

28. 28. The method of claim 27, wherein the acrylate monomer comprises 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), vinyltrimethoxysilane, vinyltriethoxysilane, or any combination thereof.

29. 29. The method of claim 27 or 28, wherein the precursor mixture further comprises an initiator.

30. 29. The method of claim 28, wherein the initiator comprises dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, cumyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, azobisisobutyronitrile, or any combination thereof.

31. Sb during step (a) or step (b) ２ O ３ The method of any one of claims 27 to 30, further comprising adding

32. 32. The method of any one of claims 27 to 31, wherein the blending in step (a), step (b), or both, occurs in a twin-screw extruder.

33. 33. The method of any one of claims 27 to 32, wherein the blending in step (a), step (b), or both, occurs at a temperature of from about 160°C to about 230°C.

34. The method of any one of claims 27 to 33, further comprising: (c) curing the flame retardant composition in water.

35. 35. The method of claim 34, wherein the curing is carried out for about 1 hour to about 10 days.

36. The method of claim 34 or 35, wherein the curing is carried out at a temperature of from about 25°C to about 200°C.

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