Modified brominated polystyrene as compatible flame retardant for polymer compositions

Abstract

In one aspect, the disclosure relates to a flame retardant composition comprising a 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 with the brominated polystyrene alone. In some aspects, the first portion and the second portion of the second polymer can be selected from the group consisting of 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 sufficiently mixed and have excellent properties, and can optionally include crosslinking to increase mechanical strength. Also disclosed herein are methods for preparing the compositions and articles of manufacture comprising the compositions.

Description

Background Art

[0001] Various commercial polymers (such as polyolefins, polystyrenes, polyesters and polyamides) from commodity plastics to engineering plastics are widely used in many applications due to their multifunctional properties. However, poor flame retardancy may hinder their use in some applications. This is because when the polymer is exposed to fire, the covalently bonded hydrocarbon backbone decomposes and burns. There are various types of flame retardant materials that can impart fire resistance to polymers. Among many types of flame retardants, halogen compounds are widely used in polyolefins due to their advantages such as cost-effectiveness, good processability and high flame retardancy. The reason why brominated flame retardants (BrFRs) are effective is mainly due to the acceptable range of bond energy between aliphatic or aromatic carbon and bromine. The bond energy is neither too high nor too low, so that they are decomposed and neutralize the hydrogen or hydroxyl radicals generated by the fire.

[0002] Among the different types of BrFR, brominated polystyrene (BPS) is a polymer BrFR with superior characteristics such as excellent thermal stability. However, BPS causes a decrease in the mechanical properties of the polyolefin into which it is incorporated, such as tensile strength, flexural strength, and impact strength. Under impact conditions, the fracture toughness value (critical energy release rate, G) of polypropylene containing BrFR is Ic ) showed a significant reduction of up to 50% compared to pure polypropylene.

[0003] Despite progress in flame-retardant material research, there remains a lack of compositions containing both brominated polystyrene as a flame retardant and a polymer typically considered incompatible with brominated polystyrene, wherein the compositions mix well and exhibit excellent mechanical properties. Such compositions would be particularly useful as coatings for cables and wires, as well as components for other articles. The present disclosure addresses these and other needs. Summary of the Invention

[0004] In accordance with the purposes of the present disclosure as embodied and broadly described herein, the present disclosure relates, in one aspect, to a flame retardant composition comprising a 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 does not react with the brominated polystyrene. In some aspects, the first portion and the second portion 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 and has excellent properties, and can optionally include crosslinking to increase mechanical strength. Also disclosed herein are methods for preparing the composition and articles comprising the composition.

[0005] Other systems, methods, features, and advantages of the present disclosure will be or will become apparent to those skilled in the art upon review of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this specification, be within the scope of the present disclosure, and be protected by the appended claims. Furthermore, all optional and preferred features and modifications of the described embodiments may be applied to all aspects of the disclosure taught herein. Furthermore, the individual features of the appended claims and all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Many aspects of the present disclosure may be better understood with reference to the following drawings. The components in the drawings are not necessarily drawn to scale, but emphasis is placed on clearly illustrating the principles of the present disclosure. Additionally, in the drawings, like reference numerals indicate corresponding parts throughout the several views.

[0007] Figure 1 The calculation of M in XLPE / gBPS-0.4 wt% polymer blends is shown. n ratio 1 H NMR spectroscopy.

[0008] Figure 2 The calculation of M in XLPE / gBPS-2.1 wt% polymer blends is shown. n ratio 1 H NMR spectroscopy.

[0009] Figure 3 Schematic diagram showing that conventional mixtures of brominated polystyrene and polyolefin resins cannot be fully mixed (left), but modified brominated polystyrene can be fully blended with polyolefins and other resins.

[0010] Figure 4A is a schematic diagram showing brominated polystyrene in one potential modified form to contain reactive groups such as trimethoxysilyl groups, and Figure 4B is a schematic representation of a commercial resin, which may include, but is not limited to, a polyolefin, which has also been modified to contain reactive groups such as trimethoxysilyl groups.

[0011] Figure 5 is a brominated polystyrene showing an embodiment of the flame retardant composition as described herein (see Figure 4A ) and commercial resins (see Figure 4B ) schematic diagram of the cross-linking of reactive groups on.

[0012] Additional advantages of the present invention will be set forth in part in the description that follows and in part will be obvious from the description, or may be learned by practice of the present invention. The advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only and do not limit the invention as claimed. DETAILED DESCRIPTION

[0013] The present disclosure provides flame retardant compositions, methods for preparing the flame retardant compositions, and articles incorporating the flame retardant compositions. The present disclosure is advantageous because it utilizes flame retardants that do not bioaccumulate and do not cause health problems for humans or animals. This can be particularly important because the flame retardant compositions can be used as coverings for cables and wires, which may be exposed to the environment. The flame retardant compositions have a uniform composition that enables the manufacture of articles having improved mechanical properties compared to materials currently used for molded parts and cable or wire applications. The flame retardant compositions can also have an improved appearance, including improved gloss.

[0014] Disclosed herein is a flame retardant composition comprising a brominated polystyrene modified by a first portion of a second polymer. In some aspects, the composition further comprises at least a second portion of the second polymer that is unreactive in the presence of the brominated polystyrene. In one aspect, 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.

[0015] In one aspect, when the first portion and the second portion 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 terephthalamide / d,4'-diphenylether terephthalamide); PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-xylenesebacamide), poly(m-xylene adipamide), copolymers thereof, or any combination thereof. In another aspect, when the first portion and the second portion of the second polymer comprise a polyolefin, the polyolefin is or comprises a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a very low density polyethylene (VLDPE), an ultra low density polyethylene (ULDPE), a medium density polyethylene (MDPE), a polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), an ethylene-octene copolymer, a stereoblock PP, an olefin block copolymer, a propylene-butane copolymer, a polyisobutylene (PIB), a poly(α-olefin), an ethylene propylene rubber (EPR), an ethylene propylene diene monomer rubber (EPDM rubber), a high density polyethylene (HDPE), an ultra high density polyethylene (UHDPE), a cross-linked polyethylene (PEX or XLPE), or any combination thereof. In yet another aspect, when the first and second parts 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 (PCTG), or any combination thereof. In yet another aspect, when the first and second parts 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.

[0016] In another aspect, the brominated polystyrene comprises a plurality of monomeric units having the structure of Formula I:

[0017]

[0018] wherein x in each monomeric unit of the plurality of monomeric units is independently 0 to 4;

[0019] wherein R1 in each monomer unit of the plurality of monomer units is independently selected from hydrogen, bromine, NR1a R 1b or a side group comprising at least 2 carbons;

[0020] where R 1a and R 1b Independently selected from C1 to C30 straight or branched chain hydrocarbons;

[0021] And wherein R2 in each monomeric unit in the plurality of monomeric units is independently selected from hydrogen or a side group comprising at least 2 carbons.

[0022] Furthermore, in this aspect, the side groups attached to R1 and / or R2 can include 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.

[0023] Also disclosed herein is a flame retardant composition wherein each R1 is hydrogen or bromine and each R2 is independently hydrogen or a side group containing at least 2 carbons. In another aspect, each R2 is hydrogen and each R1 is independently hydrogen, bromine or a side group containing at least 2 carbons.

[0024] In one aspect, the average value of x over a plurality of monomeric units is from about 2 to about 5, or from about 2 to about 4, or from about 2 to about 3, or is 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. Additionally, in this aspect, x can be an integer, or can be a fraction or a decimal value rather than an integer.

[0025] In one aspect, about one pendant group containing at least 2 carbons is present at R1 or R2 at a level of 0 to 250 of the total monomer units. In the brominated polystyrene represented in Formula I, the pendant group can be present 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 (or a combination of any of the foregoing values, or a range encompassing any of the foregoing values) of the monomer units in the plurality of monomer units.

[0026] In another aspect, the disclosed flame retardant composition comprises from about 0 wt% to about 2.1 wt% of pendant groups, about 0 wt% to 0.75 wt%, about 0.5 wt% to 0.7 wt%, about 1 wt% to 2 wt%, or about 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, or about 2.1 wt% of pendant groups, based on the total weight of the brominated polystyrene, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0027] In some aspects, the side group having at least 2 carbon atoms of at least one monomeric unit in the plurality of monomeric units comprises a trimethoxysilyl group. In one aspect, the side group may be selected from or any combination thereof.

[0028] In one aspect, the first portion of the second polymer comprises at least one pendant group comprising a trimethoxysilyl group. In yet another aspect, the flame retardant composition comprises at least one crosslink between a trimethoxysilyl group on the brominated polystyrene and a trimethoxysilyl group in the first portion of the second polymer.

[0029] In certain embodiments, a pendant group at R1 or R2 in Formula I as described can be introduced into the brominated polystyrene during the modification reaction.

[0030] In certain embodiments, acrylate or vinyl monomers having pendant groups comprising 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, can be polymerized during the modification reaction to form an oligomer or homopolymer having at least 2 repeating units.

[0031] In some aspects, these acrylate or vinyl oligomers or homopolymers have from 2 to 1000 repeat units, including any integer number of repeat units within this range. The oligomers and homopolymers present can all have different numbers of repeat units, they can have the same number of repeat units, or they can have any distribution of repeat units within this range.

[0032] In some aspects, the flame retardant composition disclosed herein may also include a synergist. On the other hand, the synergist may be antimony trioxide (Sb herein O or ATO) or another synergist. In yet another aspect, the flame retardant composition may 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 % Sb O or other synergists, or about 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt % or about 10 wt % Sb O or other synergists, any combination of the foregoing values, or the scope of any of the foregoing values.

[0033] In some aspects, the disclosed compositions further comprise a filler, such as, for example, talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH) 3, AlO(OH), Mg(OH) 2, kaolinite, wollastonite, mica, glass beads, or any combination thereof. In one aspect, the disclosed compositions further comprise a reinforcing agent, such as, for example, glass fiber.

[0034] In one aspect, disclosed herein are articles comprising the disclosed flame retardant compositions. In one aspect, the articles have a flammability rating of V0 according to test method UL94. In one aspect, the articles can include molded parts for housings, connectors, and / or circuit boards for electronic devices, various automotive applications such as engine compartment parts, seats, insulation materials, and interior components, and residential applications including insulation materials, carpets, and wall coverings. In another aspect, the articles can be coverings for cables and / or wires. In yet another aspect, the disclosed articles can be or include textiles and / or adhesives.

[0035] The present disclosure provides a method for preparing a flame retardant composition. In one aspect, the method comprises blending an acrylate monomer with brominated polystyrene to form a precursor mixture. The blending step can be performed for a period of about 0.1 minute to about 30 minutes, or about 0.1 minute to about 5 minutes, about 5 minutes to about 15 minutes, or about 15 minutes to about 30 minutes, or can be about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. 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°C to about 200°C, about 200°C to about 230°C, or at a temperature of about 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, or about 230°C (or a combination of any of the foregoing values, or a range encompassing any of the foregoing values).

[0036] 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 performed for a period of time of about 0.1 minute to about 30 minutes, or about 0.1 minute to about 5 minutes, about 5 minutes to about 15 minutes, or about 15 minutes to about 30 minutes, or can be about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. 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°C to about 200°C, about 200°C to about 230°C, or at a temperature of about 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, or about 230°C (or a combination of any of the foregoing values, or a range encompassing any of the foregoing values).

[0037] The brominated polystyrene having the first portion of the second polymer can then be blended with the second portion of the second polymer. This blending step can be performed for a period of time 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 can be about 0.1, 1, 2, 5, 10, 15, 20, 25, or about 30 minutes, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. 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° C. to about 200° C., about 200° C. to about 230° C., or at about 160° C., 165° C., 170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 205° C., 210° C., 215° C., 220° C., 225° C., or about 230° C. (or a combination of any of the foregoing values, or a range encompassing any of the foregoing values). Synergists, such as, for example, antimony trioxide, can be added during any part of the mixing process.

[0038] The method may also be optionally included in water-cured flame retardant compositions. Curing may be carried out from about 1 hour to about 10 days, or from about 1 hour to about 24 hours, from about 1 day to about 5 days, or from about 5 days to about 10 days, or from about 1, 2, 6, 12, 18 or 24 hours, or from about 2, 3, 4, 5, 6, 7, 8, 9 or about 10 days, or a combination of any preceding values, or encompass the scope of any preceding values. In another aspect, curing may be carried out from about 25°C to about 200°C, from about 25°C to about 50°C, from about 50°C to about 75°C, or from about 75°C to about 100°C, or at a temperature of about 25°C, 50°C, 100°C, 150°C or about 200°C (or a combination of any preceding values, or encompass the scope of any preceding values).

[0039] In one aspect, 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 substances used by those skilled in the art of moisture-curable wire and cable production, or combinations thereof. In some aspects, the precursor mixture further includes an initiator, such as, for example, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, cumene hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, azobisisobutyronitrile, or any combination thereof.

[0040] In certain embodiments, brominated polystyrene can be modified to include reactive groups by reactive extrusion according to the procedure shown in Scheme 1A or Scheme 1B. A schematic diagram of this process is shown in Figure 4A middle.

[0041]

[0042] In certain embodiments, a resin, such as, for example, a polyolefin resin, can be modified to include reactive groups by reactive extrusion according to the procedure shown in Scheme 2. A schematic diagram of this process is shown in Figure 4B middle.

[0043]

[0044] In certain embodiments, the grafted brominated polystyrene and the resin can be crosslinked by aqueous curing or another method according to the procedure shown in Scheme 3. A schematic diagram of this process is shown in Figure 5 middle.

[0045]

[0046] Schemes 4 to 7 depict some of the many modifications and other embodiments disclosed herein that will occur to those skilled in the art of the disclosed compositions and methods having the benefit of the teachings presented in the foregoing description and associated drawings. It should be understood, therefore, that this disclosure is not limited to the specific embodiments disclosed, and that such 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 aspects described herein. Such variations and adaptations are intended to be included within the teachings of this disclosure and to be encompassed by the claims herein.

[0047]

[0048]

[0049] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0050] As will be apparent to those skilled in the art after reading this disclosure, each individual embodiment described and illustrated herein has discrete components and features that may be readily separated or combined with the features of any other several embodiments without departing from the scope or spirit of the disclosure.

[0051] Any described method may be performed in the order of events recited, or in any other order that is logically feasible. That is, unless expressly stated otherwise, it is not intended that any method or aspect described herein be construed as requiring that its steps be performed in a specific order. Therefore, when a method claim does not expressly state in the claim or specification that the steps are to be limited to a specific order, no order is intended to be inferred in any respect. This applies to any possible non-express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, obvious meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0052] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials relevant to the publications cited. The publications discussed herein are provided only for their disclosures before the date of filing this application. Any content herein should not be construed as admitting that the present invention has no right to rely on prior inventions and earlier than such publications. In addition, the publication date provided herein may be different from the actual publication date, and they may need to be confirmed separately.

[0053] Although aspects of the disclosure may be described and claimed using specific legal categories, such as the system legal category, this is for convenience only, and those skilled in the art will understand that aspects of the disclosure may be described and claimed using any legal category.

[0054] It should also be understood that the terminology used herein is for the purpose of describing specific aspects only and is not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the specification and the context of the relevant art, and should not be interpreted as idealized or overly formal unless explicitly defined herein.

[0055] Before describing the various aspects of the present disclosure, the following definitions are provided and shall apply unless otherwise indicated.Additional terms may be defined elsewhere in this disclosure.

[0056] definition

[0057] As used herein, "comprising" should be interpreted as indicating the presence of stated features, integers, steps or components as mentioned, but does not exclude the presence or addition of one or more features, integers, steps or parts thereof or groups thereof. In addition, each of the terms "by", "comprising", "comprises", "comprised of", "including", "includes", "included", "involving", "involves", "involved", and "such as" is used in its open, non-restrictive sense and is used interchangeably. In addition, the term "comprising" is intended to include instances and aspects encompassed by the terms "substantially consisting of" and "consisting of". Similarly, the term "substantially consisting of" is intended to include instances encompassed by the term "consisting of".

[0058] 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," "polyamide," or "filler" includes but is not limited to a mixture or combination of two or more such monomers, polyamides, or fillers, etc.

[0059] It should be noted that ratio, concentration, amount and other numerical data can be expressed in range format in this article. It should be further understood that the endpoints of each range are meaningful relative to another endpoint and independently of another endpoint. It should also be understood that multiple values ​​are disclosed herein, and each value is also disclosed as "about" the specific value in addition to the value itself. For example, if the value "10" is disclosed, "about 10" is also disclosed. Scope can be expressed as from "about" a specific value and / or to "about" another specific value in this article. Similarly, when a value is expressed as an approximate value by using the antecedent "about", it will be understood that the specific value forms another aspect. For example, if the value "about 10" is disclosed, "10" is also disclosed.

[0060] When expressing a range, additional aspects include from one specific value and / or to another specific value. For example, when the stated range includes one or both of the limits, the present disclosure also includes a range that excludes any one or both of those included limits, for example, the phrase "x to y" includes a range from 'x' to 'y' and a range greater than 'x' and less than 'y'. A range can also be expressed as an upper limit, such as 'about x, y, z or less', and should be interpreted as including a specific range of 'about x', 'about y' and 'about z', as well as a range of 'less than x', 'less than y' and 'less than z'. Similarly, the phrase 'about x, y, z or more' should be interpreted as including a specific range of 'about x', 'about y' and 'about z', as well as a range of 'greater than x', 'greater than y' and 'greater than z'. In addition, the phrase "about 'x' to 'y'" (wherein 'x' and 'y' are numerical values) includes "about 'x' to about 'y'".

[0061] It should be understood that this range format is used for convenience and brevity and should therefore be interpreted flexibly to include not only the values ​​explicitly recited as the limits of the range, but also all individual numbers or subranges encompassed within the range, as if each value and subrange were explicitly recited. For illustration, 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 the individual values ​​(e.g., about 1%, about 2%, about 3%, and about 4%) and subranges within the specified range (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% and other possible subranges).

[0062] As used herein, the terms "about," "approximately," "at or about," and "substantially" mean that the amount or value in question can be an exact value or a value that provides an equivalent result or effect as described in the claims or taught herein. That is, it should be understood that amounts, dimensions, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as necessary to reflect tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, so that an equivalent result or effect is achieved. In some cases, it is not possible to reasonably determine a value that provides an equivalent result or effect. In such cases, it should generally be understood that, as used herein, unless otherwise indicated or inferred, "about" and "at or about" are intended to indicate a nominal value with a ±10% variation. In general, an amount, dimension, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "at or about," regardless of whether such an explicit statement is made. It should be understood that when "about," "approximately," or "at or about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless otherwise specifically stated.

[0063] As used herein, the term "effective amount" refers to an amount sufficient to achieve the desired modification of the physical properties of a composition or material. For example, an "effective amount" of brominated polystyrene refers to an amount sufficient to achieve the desired improvement in properties regulated by the formulation components, such as achieving a desired level of flame retardancy while maintaining good mechanical properties. The specific level expressed as wt% in the composition required as an effective amount will depend on a variety of factors, including the amount and type of polymer, the amount and type of brominated polystyrene (including the degree of substitution with bromine atoms), the amount and type of any filler used, and the end use of the article made using the composition.

[0064] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0065] "Test method UL94" refers to a test method developed by Underwriters Laboratories (UL) in the United States, which is intended to serve as a preliminary indication of the acceptability of a plastic for use as part of an article with respect to flammability. To achieve a V-0 flammability rating, for example, after two 10-second flames are applied to the test rod, combustion of the article must cease within 10 seconds. Flaming drips may not be present.

[0066] Unless otherwise indicated, temperatures referred to herein are based on atmospheric pressure (ie, one atmosphere).

[0067] Now that aspects of the present disclosure have been described, generally speaking, the following examples describe some additional aspects of the present disclosure. Although aspects of the present disclosure are described in conjunction with the following examples and corresponding text and drawings, it is not intended that aspects of the present disclosure be limited to this description. On the contrary, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.

[0068] Example

[0069] The following examples are presented to provide a complete disclosure and description of how the compounds, compositions, articles, devices and / or methods claimed herein are prepared and evaluated by one of ordinary skill in the art, and are intended to be purely exemplary of the present disclosure and are not intended to limit the scope of what the inventors consider to be their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be considered. Unless otherwise indicated, parts are by weight, temperatures are in ° C. or at ambient temperature, and pressures are equal to or near atmospheric pressure.

[0070] Example 1: Preparation of XLPE / gBPS-0.4wt% polymer blend

[0071] Modification reaction

[0072] Dicumyl peroxide (DCP, 0.163 g) solid was dissolved in 0.326 g of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA). This TMSPMA / DCP solution was then manually mixed with 6.20 g of BPS powder. The mixture was added to a twin extruder (ThermoFisher Scientific HAAKE MiniCTW micro-tapered twin-screw compounder) and blended at 185°C for 10 minutes. The screw speed was 300 rpm. This yielded 6.21 g of the modified product, rBPS (reactive BPS).

[0073] Calculation of polymer ratio

[0074] The modified product rBPS (0.5 g) was dissolved in 5 mL of THF (tetrahydrofuran) by ultrasonic treatment. The solution was then added dropwise to 50 mL of methanol solvent under stirring. rBPS precipitated out. The solution was filtered and the rBPS precipitate was collected. The purification process was repeated twice to remove the residual unreacted TMSPMA monomer and DCP decomposition products. The rBPS precipitate was dried in a vacuum oven at 120°C overnight. The proton nuclear magnetic resonance (NMR) was used to analyze the rBPS precipitate. 1 1H NMR) to calculate the polymer ratio of rBPS. 100 mg of purified rBPS was dissolved in 1 mL of deuterated chloroform (CDCl3), and the solution was used to 1 H NMR measurements. BPS has a bromine content of 68.5 wt.%, meaning that within each repeating unit of the BPS chemical structure, 2.75 Br atoms and 2.25 H atoms are attached to the benzene ring of BPS. The molar mass of the BPS repeating unit is 321 g / mol, while the molar mass of TMSPMA is 248 g / mol. The proton atoms in the trimethoxy group of TMSPMA were selected as characteristic peaks for calculations. 1 H NMR results showed Figure 1 The calculation procedure is as follows:

[0075] For every nine proton atoms in the trimethoxy group (chemical shift δ = 3.60), there are 445.8 proton atoms attached to the phenyl ring of BPS (δ = 5.6 to 8.0). This means that when TMSPMA molecules are present in the rBPS polymer chain, there are (445.8 x 0.98) / 2.25 = 194 BPS repeating units. Note that a factor of 0.98 is used here to account for the contribution of the peak area from deuterated chloroform. The polymer ratio is then calculated, i.e., w(TMSPMA) / w(rBPS) or w(TMSPMA) / (w(TMSPMA) + w(BPS)):

[0076] 248 / (248+194×321)=0.004=0.4 wt%.

[0077] The rBPS product having a polymer ratio of 0.4 wt% was named rBPS-0.4 wt%.

[0078] Preparation of XLPE / rBPS-0.4wt% polymer blends

[0079] and 1 The purification process for the H NMR measurement was different. The rBPS product obtained in step 1 was placed in a vacuum oven (10 mmHg / 180°C / 1 hour) to remove residual TMSPMA monomer. The purified rBPS was then used for polymer blending as follows:

[0080] First, crosslinkable polyethylene (rPE) (LyondellBasell AQUATHENE 120000, 39.0 g) and rBPS-0.4 wt.% (13.0 g) were blended in a twin-screw Haake mixer (Haake Buchler Rheocord system 40) at 225° C. for 7 minutes. This blend was further blended with a catalyst masterbatch (LyondellBasell AQUATHENE CM04482, 2.6 g) at 185° C. for 7 minutes, with a weight composition of rPE / rBPS / catalyst = 75 / 25 / 5. The rPE / rBPS / catalyst blend was injection molded into rectangular bars 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 an oven at 90°C overnight; the methoxysilane groups should react with each other during this water curing step and ultimately obtain a crosslinked sample, ie, the XLPE / rBPS-0.4 wt% polymer blend.

[0081] The Izod test shows an impact strength of 5.88kJ / m2, compared to 8.5kJ / m2 for XLPE / BPS. 2 , and the impact strength of XLPE is 84.8kJ / m 2 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 the Izod impact and hot creep tests can be found in Example 6.

[0082] Example 2: Preparation of XLPE / rBPS-2.1 wt% polymer blend

[0083] 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 same calculation procedure as in Example 1 was followed using Figure 2 As shown in 1 The grafting rate was calculated based on the H NMR results.

[0084] XLPE / gBPS-2.1 wt. % polymer was prepared as in Example 1 using 39.0 g rPE, 13.0 g rBPS-2.1 wt. % and 2.6 g catalyst masterbatch.

[0085] Izod test showed 8.81kJ / m 2 The impact strength of XLPE / BPS is 8.5kJ / m 2 , and the impact strength of XLPE is 84.8kJ / m 2 Hot creep testing showed an elongation of 5% ± 2%, compared to 5% ± 2% for XLPE / BPS and 7% ± 2% for XLPE.

[0086] Example 3: Preparation of PP / rBPS2(BPS-g-AMEH) / EBA-g-MAH polymer blends

[0087] Modification reaction

[0088] Dicumyl peroxide (DCP, 0.7 g), 2-aminoethyl methacrylate hydrochloride (AMEH, 3.5 g), and 65.8 g of BPS powder were manually mixed in a plastic bag. The mixture was loaded 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 collected from the internal mixer. The resulting material was a mixture of rBPS2 (reactive BPS2, BPS-g-AMEH) and poly(AMEH), as generally shown in Scheme 4.

[0089] Preparation of PP / rBPS2 / EBA-g-MAH polymer blends

[0090] 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 Polymer, 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 test bars using a ThermoFisher Minijet pro at an injection molding pressure of 670 psi, a barrel temperature of 230° C., a mold temperature of 50° C., and a cooling time of 10 seconds.

[0091] 43 g PP (LyondellBasell, Prfoax-6523), 5 g unmodified BPS and 2 g 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.

[0092] The room temperature Izod impact test showed that the impact strength of PP / rBPS2 / EBA-g-MAH was 5.9 kJ / m2, which was 12% higher than the 4.8 kJ / m2 impact strength of PP / BPS / EBA-g-MAH. The morphological observation results of PP / BPS / EBA-g-MAH and PP / rBPS2 / EBA-g-MAH by transmission electron microscopy (JEOL-1200X) were shown in Figure 3. Figure 6A and Figure 6B The location of the elastomer (EBA-g-MAH) is significantly different between PP / BPS / EBA-g-MAH and PP / rBPS2 / EBA-g-MAH. For PP / BPS / EBA-g-MAH, EBA-g-MAH is dispersed separately ( Figure 6A On the other hand, for PP / rBPS2 / EBA-g-MAH, EBA-g-MAH surrounds rBPS2 ( Figure 6B ).

[0093] Example 4: Preparation of PPA / rBPS3 polymer blends

[0094] Preparation of rBPS3 (BPS-g-GMA)

[0095] Dicumyl peroxide (DCP, 22.68 g) and glycidyl methacrylate (GMA, 45.46 g) were premixed with 2199.96 g of BPS powder. The premixed mixture was fed into a Werner & Pfleider (Coperion) ZSK-30 twin-screw extruder (L / D 24, screw diameter 30 mm, barrel temperature 210° C.-235° C. from hopper to die) at a screw speed of 175 RPM and a feed rate of 14 kg / hr. A vacuum stack was used to remove unreacted GMA monomer. The manually chopped pellets produced from the die were a mixture of modified rBPS3 (reactive BPS3, BPS-g-GMA) and poly(GMA).

[0096] 39g of PPA (polyphthalamide, Dupont HTN-502, PA6T / 66 type) and 11g of rBPS3 were manually mixed in a plastic bag. The mixture was extruded in a ThermoFisher Process 11 twin-screw extruder with a feeder. The barrel temperature of the extruder was 285°C to 320°C from the hopper to the die. The twin-screw speed was 150 RPM, and the feed rate was 0.2kg / h. The extruded strands were cooled in a conveyor belt and then chopped by a pelletizer. The chopped pellets after extrusion were used for injection molding of izod rods via a ThermoFisher Minijet pro at an injection pressure of 3,450psi, a barrel temperature of 345°C, a mold temperature of 90°C, and a cooling time of 15 seconds. The PPA / BPS polymer blend (39 g PPA and 11 g unmodified BPS) was extruded and injection molded in the same manner as the PPA / rBPS3 polymer blend.

[0097] Room temperature Izod impact testing showed that the impact strength of PPA / rBPS3 was 2.8 kJ / m2, which was 40% higher than the 2.0 kJ / m2 impact strength of PPA / BPS. The average particle size and total number of BPS dispersed in PPA / rBPS3 were 0.23 μm and 45 ( Figure 8A and Figure 8B ), which has better dispersibility. In contrast, the average particle size and total number of BPS dispersed in PPA / BPS are 2.08 μm and 7 ( Figure 7A and Figure 8B ).

[0098] Example 5: Preparation of PPA / rBPS4 polymer blends

[0099] Preparation of rBPS4 (BPS-g-MAH)

[0100] Dicumyl peroxide (DCP, 22.68 g) and maleic anhydride (GMA, 36.29 g) were premixed with 2209.3 g of BPS powder. The final material was produced in the same manner as described for the preparation of rBPS3. The resulting material was a mixture of rBPS4 (reactive BPS4, BPS-g-MAH), poly(MAH), etc., which contained 1,2,3,4-cyclobutanetetracarboxylic dianhydride, carbon dioxide, and polyvinylene ketone anhydride, as well as other potential ring-opening and branching structures that would be apparent to those skilled in the art.

[0101] 39 g PPA and 11 g rBPS4 were mixed manually in a plastic bag. The mixture was extruded and injection molded in the same manner as described for the preparation of the PPA / rBPS3 polymer blend.

[0102] The room temperature Izod impact test showed that the impact strength of PPA / rBPS4 was 2.9 kJ / m2, which was 45% higher than the 2.0 kJ / m2 impact strength of PPA / BPS. The average particle size and total number of BPS dispersed in PPA / rBPS4 were 0.02 μm and 271 ( Figure 9A and Figure 9B ), which has better dispersibility. In contrast, the average particle size and total number of BPS dispersed in PPA / BPS are 2.08 μm and 7 ( Figure 7A and Figure 8B ).

[0103] Example 6: Testing Procedure

[0104] Room temperature and low temperature notched Izod impact testing

[0105] For room temperature Izod impact testing, one day after its injection molding, injection molded Izod rods (63.5mm×10.2mm×3.2mm with a V-notch depth of 10.16mm) were subjected to Izod impact testing at 25°C with a 2.7J pendulum weight. For low temperature Izod impact testing, fully cross-linked V-notch rectangular rods (63.5mm×10.2mm×3.2mm with a V-notch depth of 10.16mm) were dried overnight in a vacuum oven before testing. They were pre-cooled for 1 hour in an environmental chamber at -37°C. These rods were then immediately tested / impacted with an 11.3J pendulum weight. The energy absorption generated was read. Izod impact strength was calculated as follows: Izod impact strength=energy absorption / cross-sectional area.

[0106] Thermal creep test

[0107] Before the test, the tensile rod (specification is 3.0mm width × 3.2mm thickness) is dried in a vacuum oven overnight. The thermal creep test is carried out according to UL-44 and UL-2556 standards. Before the test, the gauge length of the tensile rod is measured and set to 1.0. The rod is preheated in an oven (150°C) and then a load stress of 0.2MPa is applied by hanging a 196g object. The rod is tested under these conditions (150°C / 0.2MPa / 15 minutes). After 15 minutes, the instantaneous length L is measured. The elongation is calculated by (L-L0) / L0. In this test, low creep is desired.

[0108] Dynamic mechanical analysis

[0109] The specimens (35 mm x 8 mm x 3.2 mm) were tested using a TA Instruments ARES-G2 rheometer at a ramp rate of 10° C. / min from 30° C. to 200° C. The test frequency was 1 Hz, and a small strain of 0.1% was applied.

[0110] Particle size analysis

[0111] The dispersed BPS phase in the processed images was manually elliptical-selected from transmission electron microscopy images taken with an EOL JEM-1400 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.

[0112] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementation forms set forth for a clear understanding of the principles of the present disclosure. Many variations and modifications may be made to the above-described embodiments without departing substantially from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included within the scope of the present disclosure and are protected by the following claims.

[0113] References

[0114] 1. Li, HM; et al, 2002, Polymer, 43: 5455-5461.

[0115] 2. Passaglia, E.; et al, 2004, Macromol Symp, 218: 61-70.

[0116] 3.Won Ho Jo, et al, 1996, Polymer, 37: 1709-1714.

Claims

1. A flame retardant composition comprising 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. The flame retardant composition of claim 1 or 2, wherein the first portion and the second portion of the second polymer comprise polyamides, polyolefins, polyesters, styrenic polymers or copolymers, or any combination thereof.

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); co-poly(p-phenylene terephthalamide / d,4'-diphenyl ether terephthalamide); PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-phenylene sebacate), poly(m-phenylene adipamide), copolymers thereof, or any combination thereof.

5. The flame retardant composition of claim 3 or 4, wherein the polyolefin comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra 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. 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(cyclohexylenedimethylene terephthalate) (PCT), polylactic acid (PLA), polycaprolactone (PCL), polyethylene terephthalate glycol (PETG), polycyclohexylenedimethylene terephthalate (PCTG), or any combination thereof.

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

8. The flame retardant composition of any one of claims 1 to 7, wherein the brominated polystyrene comprises a plurality of monomer units having the structure of Formula I: wherein x in each monomeric unit of the plurality of monomeric units is independently 0 to 4; wherein R1 in each monomer unit of the plurality of monomer units independently comprises hydrogen, bromine, NR 1a R 1b or a side group comprising at least 2 carbons; where R 1a and R 1b Independently selected from C1 to C30 straight or branched chain hydrocarbons; And wherein R2 in each monomeric unit in the plurality of monomeric units independently comprises hydrogen or a pendant group comprising at least 2 carbons.

9. The flame retardant composition of any one of claims 1 to 8, wherein each R1 is hydrogen or bromine, and each R2 is independently hydrogen or said pendant group comprising at least 2 carbons, provided that at least one pendant group is present in said first portion of said second polymer.

10. The flame retardant composition of any one of claims 1-8, wherein each R2 is hydrogen, and each R1 is independently hydrogen, bromine, or said pendant group comprising at least 2 carbons, provided that at least one pendant group is present in said first portion of said second polymer.

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

12. The flame retardant composition of any one of claims 1-11, wherein there is about 1 pendant group comprising at least 5 carbons at R1 or R2 for every 5 to 150 monomer units in the plurality of monomer units.

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

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

15. The flame retardant composition of any one of claims 8 to 14, wherein the pendant group comprising at least 2 carbons at R1 or R2 of at least one monomer unit in the plurality of monomer units comprises a trimethoxysilyl group.

16. The flame retardant composition of claims 13-15, wherein the side group comprising at least 5 carbons has a structure selected from the group consisting of: or any combination thereof.

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

18. The flame retardant plastic composition according to any one of claims 1 to 17, further comprising Sb2O3.

19. The flame retardant plastic composition of claim 18, wherein the flame retardant plastic composition comprises about 1 wt% to about 10 wt% Sb2O3.

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

21. The flame retardant composition of claim 20, wherein the filler comprises talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH)3, AlO(OH), Mg(OH)2, 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. 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 1-23.

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

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

27. A method for preparing the flame retardant composition according to any one of claims 2 to 23, the method comprising: (a) admixing an acrylate monomer comprising at least 2 carbon atoms with a brominated polystyrene to form a precursor mixture, and blending the precursor mixture to produce the brominated polystyrene modified by the presence of a first portion of a second polymer; as well as (b) blending the brominated polystyrene grafted to the first portion of the second polymer with a second portion of the second polymer.

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

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

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

31. The method of any one of claims 27-30, further comprising adding Sb2O3 during step (a) or step (b).

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

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

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

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

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

Images