Encapsulated flame retardant compositions, methods for making encapsulated flame retardant compositions, and articles comprising encapsulated flame retardant compositions

Abstract

In one embodiment, the present disclosure relates to a flame-retardant plastic composition, the flame-retardant plastic composition comprising a polymeric component and a brominated flame retardant (BrFR), the BrFR comprising one or more particles at least partially encapsulated by a thermoplastic toughening agent. In some embodiments, the encapsulant can be in the form of a core-shell structure, the shell having an average thickness of about 5 nm to 10 μm. The thermoplastic toughening agent can be selected from styrenic block copolymers, thermoplastic polyurethanes, nitrile butadiene rubbers, acrylic elastomers, copolyester elastomers, thermoplastic polyetherester elastomers, thermoplastic amide ether elastomers, chlorinated rubbers, ionomers, thermoplastic vulcanizates, or any combination thereof. The flame-retardant plastic composition further comprises a filler and / or a compatibilizer. Also disclosed are methods for producing the flame-retardant plastic composition and articles produced from the composition.

Description

[Background technology]

[0001] Commercially available polymers, ranging from everyday items to engineering plastics (e.g., polyolefins, polystyrene, polyesters, and polyamides), are widely used in many industrial applications due to their diverse properties. However, their low flame retardancy precludes their use in some applications. This is due to the relatively low limiting oxygen index (LOI) of most polymers. When a polymer is exposed to fire, the covalently bonded backbone decomposes and burns. There are various types of flame-retardant materials that can impart flame-retardant 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 particularly effective because the bond energy between aliphatic (or aromatic) carbon and bromine is in a favorable range. BrFRs have a bond energy that is neither too high nor too low to decompose and neutralize the hydrogen or hydroxyl radicals generated by combustion.

[0002] Brominated polystyrene (BPS), one of the common BrFRs, reduces the mechanical properties of polyolefins, such as tensile strength, flexural strength, and impact strength, when incorporated. The fracture toughness (critical energy release rate G) of polypropylene (PP) containing BrFRs has been shown to be significantly lower than that of PP. Ic) is substantially reduced by up to 50% under impact conditions compared to PP without the additive. Generally, the decrease in mechanical properties is caused by weak interfacial strength between the two different polymers in the blend. Wei et al. reported that the use of a styrene-based block copolymer that improves adhesion between PP and polyphenylene ether (Noryl) improves fracture toughness. Several simulation studies have shown that rubber-coated particles, in which hard spherical particles are coated with rubber above a certain thickness, can improve the fracture toughness of three-phase polymer composites. However, these modeling studies have limitations, such as the assumption that each interface has an ideal boundary. For hard polymer particles, their particle size varies significantly depending on the processing conditions. Furthermore, because the interfacial adhesion also depends on the processing conditions, their overall morphology simultaneously changes in ways not considered by standard models.

[0003] Despite advances in flame retardant polymer research, there remains a lack of compositions that achieve good flame retardant properties while maintaining high processability using existing equipment to yield articles with excellent mechanical properties. The present disclosure addresses these and further needs. Summary of the Invention

[0004] In accordance with the objective(s) of the disclosure as embodied and broadly described herein, the disclosure, in one aspect, relates to a flame-retardant plastic composition comprising a polymeric component and a brominated flame retardant, wherein the brominated flame retardant is comprised of one or more particles at least partially encapsulated by a thermoplastic toughening agent. In some aspects, the encapsulant can be in the form of a core-shell structure, the shell having an average thickness of about 5 nm to about 10 μm. The thermoplastic toughening agent can be a thermoplastic elastomer, such as a styrenic block copolymer (with or without maleic anhydride grafts), a thermoplastic polyurethane, a nitrile butadiene rubber, an acrylic elastomer, a copolyester elastomer, a thermoplastic polyetherester elastomer (TPEE), a thermoplastic amide ether elastomer (TAEE), a chlorinated rubber, an ionomer, a thermoplastic vulcanizate, a polyolefin elastomer, or any combination thereof. In some aspects, the flame-retardant plastic composition further comprises a filler and / or a compatibilizer (e.g., maleic anhydride). Also disclosed are methods for making the flame retardant plastic compositions and articles made from the compositions.

[0005] Other systems, methods, features, and advantages of the present disclosure will become apparent to those skilled in the art upon examination of the following figures and detailed description. All such additional systems, methods, features, and advantages are intended to be encompassed by this specification, be within the scope of this disclosure, and be protected by the accompanying claims. Furthermore, any preferred features and modifications of the described embodiments can be utilized in all aspects of the present disclosure taught herein. Furthermore, the individual features of the dependent claims, and any preferred features and modifications of the described embodiments, can be combined with or substituted for one another.

[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. [Brief explanation of the drawings]

[0007] [Figure 1] A is a schematic diagram showing the geometry of a single-notch three-point bend (SN3PB) specimen. B is a top and front view of an SN3PB. C is an optical microscope (OM) image showing a sharp crack. D is a top and front view of an SN3PB test to obtain the U0 term. E is an OM image showing a cracked specimen. [Figure 2A] FIG. 11 is a side view showing the formation of a sharp crack for the SN3PB and double-notched four-point bend (DN4PB) specimens below the machined slot. [Figure 2B] FIG. 1 is a cross-sectional view showing the fracture surface of an SN3PB test piece after impact fracture. [Figure 3] A is a schematic diagram showing the geometry of the DN4PB specimen. B is a top view of the DN4PB, and C is a front view of the DN4PB. D shows a petrographic thin section on a glass slide and a transmission optical microscope (TOM) image of the polypropylene (PP) at the mid-plane (plane strain region) of the specimen where the crack was arrested. [Figure 4A] TEM images showing four systems: PP / BPS[L] (Figure 4A), PP / BPS / SEBS[SD] (Figure 4B), PP / BPS[S] (Figure 4C), and PP / BPS / SEBS[CS] (Figure 4D). [Figure 4B] TEM images showing four systems: PP / BPS[L] (Figure 4A), PP / BPS / SEBS[SD] (Figure 4B), PP / BPS[S] (Figure 4C), and PP / BPS / SEBS[CS] (Figure 4D). [Figure 4C]TEM images showing four systems: PP / BPS[L] (Figure 4A), PP / BPS / SEBS[SD] (Figure 4B), PP / BPS[S] (Figure 4C), and PP / BPS / SEBS[CS] (Figure 4D). [Figure 4D] TEM images of four systems: PP / BPS[L] (Figure 4A), PP / BPS / SEBS[SD] (Figure 4B), PP / BPS[S] (Figure 4C), and PP / BPS / SEBS[CS] (Figure 4D). The numbers in the upper left corner of each image indicate the average particle size of the BPS particles in that image. Abbreviations: PP = polypropylene, BPS = brominated polystyrene, SEBS = styrene-ethylene-butylene-styrene, L = large particles, S = small particles (see Examples for size information), SD = separately dispersed particles, CS = core-shell particles. [Figure 5A] FIG. 1 is a graph showing surface energy versus surface coverage. [Figure 5B] FIG. 1 is a graph showing interfacial energy versus temperature. [Figure 5C] FIG. 10 is a graph showing the expansion coefficient SBPS·SEBS versus temperature. [Figure 5D] FIG. 10 is a graph showing the expansion coefficient SSEBS·BPS versus temperature. [Figure 5E] FIG. 1 is a diagram showing types of morphology and conditions for satisfying the types. [Figure 6A] FIG. 1 is a graph showing Izod impact strength. [Figure 6B] FIG. 1 shows the tensile strength of some model systems described herein. [Figure 7A] FIG. 1 shows a plot of energy (E) against normalized area (BDφ) for PP / BPS[L]. [Figure 7B] FIG. 1 shows a plot of energy (E) versus normalized area for PP / BPS / SEBS[SD]. [Figure 7C] FIG. 1 shows a plot of energy (E) versus normalized area for PP / BPS[S]. [Figure 7D]FIG. 1 shows a plot of energy (E) versus normalized area for PP / BPS / SEBS[CS]. [Figure 7E] FIG. 1 shows a plot of energy (E) versus normalized area for PP. [Figure 7F] FIG. 1 shows a plot of energy (E) versus normalized area for PP / SEBS. [Figure 8] A and B show TOM and POM images of PP / BPS[L], respectively. C and D show TOM and POM images of PP / BPS / SEBS[SD] at the crack-arrested area after DN4PB. [Figure 9A] The TOM image of PP / BPS[S] is shown. [Figure 9B] A polarized optical microscope (POM) image of PP / BPS[S] is shown. [Figure 9C] This shows a TOM image of the PP / BPS / SEBS[CS] crack arrested after DN4PB. [Figure 9D] This shows a POM image of the PP / BPS / SEBS[CS] in the area where the crack was arrested after DN4PB. [Figure 10] This shows the TEM observation results of the PP / BPS / SEBS[CS] in the area where the crack stopped after the DN4PB test. [Figure 11A] The TOM image of PP is shown. [Figure 11B] The POM image of PP is shown. [Figure 11C] This shows a TOM image of the PP / SEBS crack-stopped area after DN4PB. [Figure 11D] This shows a POM image of PP / SEBS in the area where the crack stopped after DN4PB. [Figure 12] FIG. 1 is a schematic diagram illustrating possible strengthening mechanisms. [Figure 13A] FIG. 1 shows a double-notched four-point bending test piece. [Figure 13B] FIG. 10 is a diagram showing the strengthening mechanism investigated by fracture surface analysis. [Figure 13C] FIG. 1 shows observation of the damaged area. [Figure 14]FIG. 1 shows the effect of SEBS rubber and processing temperature on morphology. [Figure 15] A to B are TEM images showing the 8 phr / 230°C system. [Figure 16] FIG. 1 shows complex viscosity as a function of angular frequency. [Figure 17] FIG. 1 shows Cole-Cole plots of neat polymer and LLDPE / BPS / SEBS blend systems. [Figure 18] FIG. 1 shows a representative engineering stress-engineering strain plot. [Figure 19] FIG. 1 shows notched Izod impact strength at −37° C. [Figure 20] A–D show OM images of the damaged area at the crack tip under bright field (left) and cross-polarized light (right) ((Figures 20A–20B) 8 phr / 230°C and (Figures 20C–20D) 8 phr / 185°C). [Figure 21] A to D show SEM analysis images of the fracture surfaces of LLDPE (FIG. 21A), 8 phr / 185°C (FIG. 21B), and 8 phr / 230°C (FIGS. 21C and 21D). [Figure 22A] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22B] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22C] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22D] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22E] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22F] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22G] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22H] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22I] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22J] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22K] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22L] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22M] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22N] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22O] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22P]TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22Q] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22R] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22S] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22T] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22U] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22V] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22W] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22X] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22Y] TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. [Figure 22Z]TEM images of experimental compositions are shown. The red arrow indicates the brominated flame retardant and the blue arrow indicates the thermoplastic elastomer. Specific compositions are shown in Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0008] Additional advantages of the present 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 present disclosure 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.

[0009] The present disclosure provides flame-retardant plastic compositions, methods for producing the flame-retardant plastic compositions, and articles comprising the flame-retardant plastic compositions. The flame-retardant plastic compositions of the present disclosure can be advantageous in that they can improve fracture toughness. While not intending to be bound by theory, the strengthening mechanism may include promoting craze initiation / shear band formation. Further features of the present disclosure can be provided below and in the examples.

[0010] In one aspect, the flame-retardant plastic composition can be used in articles such as molded parts for use in electronic device housings or connectors or circuit boards, various automotive applications such as engine bay components, seats, insulation, and interior components, and residential applications such as insulation, carpeting, and wall coverings. In another aspect, the article can be a cable and / or wire jacket. In yet another aspect, the disclosed articles can be used in textiles and adhesives.

[0011] In one embodiment, a flame-retardant plastic composition can include a polymer component and a brominated flame retardant. The brominated flame retardant can be composed of one or more particles, and one or more particles can be at least partially encapsulated by a thermoplastic toughening agent. The flame-retardant plastic composition can also include one or more particles that are not encapsulated by a thermoplastic toughening agent. The flame-retardant plastic composition can include particles with varying degrees of encapsulation, ranging from fully encapsulated to not encapsulated. Alternatively or additionally, one or more clusters containing two or more particles can include varying degrees of encapsulation. Thus, the flame-retardant plastic compositions provided by embodiments of the present disclosure can be quite complex, in that individual particles can be partially or fully encapsulated, clusters of two or more particles can be partially or fully encapsulated, some individual particles can be unencapsulated, and some clusters of particles can be unencapsulated. In one embodiment, the weight percent of the particles and / or clusters of particles that may be at least partially encapsulated can be about 1 to 100 weight percent, about 5 to 90 weight percent, about 15 to 75 weight percent, or about 30 to 50 weight percent of the total weight of the particles and / or clusters of particles.

[0012] In one embodiment, the one or more particles of the brominated flame retardant can be present in one or more of the following forms (i)-(v): (i) a plurality of particles that are individually partially encapsulated by the thermoplastic toughening agent, (ii) a plurality of particles that are individually fully encapsulated by the thermoplastic toughening agent, (iii) a plurality of clusters of two or more particles, where each cluster of the particles is collectively partially encapsulated by the thermoplastic toughening agent, (iv) a plurality of clusters of two or more particles, where each cluster of the particles is collectively fully encapsulated by the thermoplastic toughening agent, or (v) any combination thereof.

[0013] In any of these embodiments, the one or more particles at least partially encapsulated by the thermoplastic toughening agent have a core-shell structure, with the thermoplastic toughening agent forming a shell or partial shell and the brominated flame retardant forming a core. In one embodiment, the shell layer of the core-shell structure has a diameter of about 5 nm to about 10 μm, about 5 nm to about 1 μm, about 5 nm to about 200 nm, about having an average thickness of 100 to about 200 nm, or having an average thickness of about 5, 10, 15, 20, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or about 1000 nm (1 μm), or any combination of the above values ​​or ranges including any of the above values. In any of these embodiments, the ratio of the average thickness of the shell layer to the average length in at least one dimension of the core layer of the core-shell structure is from about 0.05:1 to about 0.25:1, from about 0.05:1 to about 0.1:1, from about 0.1:1 to about 0.2:1, or is about 0.05:1, 0.1:1, 0.15:1, 0.2:1, or about 0.25:1, or any combination of the foregoing values ​​or ranges encompassing any of the foregoing values.

[0014] In one embodiment, without wishing to be bound by theory, the thermoplastic toughening agent can coat the brominated flame retardant particles to a thickness sufficient to achieve good dispersion of the brominated flame retardant in the polymer component and to turn the brominated flame retardant into a reinforcing particle. The thermoplastic toughening agent may also act as a compatibilizer, which is further described below. In one embodiment, without wishing to be bound by theory, the toughening agent acts as an interface between the brominated flame retardant and the polymer component.

[0015] In one embodiment, the polymer component can be selected from polystyrene, 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), polyamide, polyester, styrenic polymer or copolymer, crosslinkable or crosslinked polyethylene (PEX or XLPE), or any combination thereof.

[0016] In some embodiments, when the polymer component is or includes a polyamide, the polyamide can be selected from 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), (p-phenylene / d,4'-diphenyl ether terephthalamide) copolymer, PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-xylene sebacamide), poly(m-xylene adipamide), copolymers thereof, or any combination thereof. In another embodiment, when the polymer component is or includes a polyester, the polyester can be selected from 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 polymer component is or includes a styrene-based polymer or copolymer, the styrene-based polymer or copolymer can be selected from styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), or any combination thereof. In one embodiment, the polymer component is polypropylene, polystyrene, linear low-density polyethylene (LLDPE), or ethylene-1-octene copolymer.

[0017] In another aspect, the brominated flame retardant can be selected from 1,2-bis(pentabromophenyl)ethane, brominated polystyrene, ethylene-bis-tetrabromophthalimide, decabromodiphenyl oxide, brominated polystyrene, poly(bromostyrene), polyvinyl bromide, polyvinylidene bromide, poly(2-bromoethyl methacrylate), poly(2,3-dibromopropyl methacrylate), poly(methyl-a-bromoacrylate), brominated butadiene styrene copolymer, or any combination thereof.

[0018] In one embodiment, the thermoplastic toughening agent can be a thermoplastic elastomer, such as a styrenic block copolymer, a thermoplastic polyurethane, a nitrile-butadiene rubber, an acrylic elastomer, a copolyester elastomer, a thermoplastic polyetherester elastomer (TPEE), a thermoplastic amide ether elastomer (TAEE), a chlorinated rubber, an ionomer, a thermoplastic vulcanizate, or any combination thereof. In one embodiment, when the thermoplastic toughening agent is or includes a nitrile-butadiene rubber, the nitrile-butadiene rubber can be a hydrogenated nitrile-butadiene rubber. In another embodiment, when the thermoplastic toughening agent is or includes a styrenic block copolymer, the styrenic block copolymer can be selected from a styrene-ethylene butylene-styrene block copolymer (SEBS), a maleic anhydride-grafted SEBS block copolymer, a styrene-ethylene propylene-styrene block copolymer (SEPS), or any combination thereof. In one embodiment, when the toughening agent is or comprises SEBS, the SEBS has a styrene:ethylene+butylene ratio of about 10:90 to about 70:30, about 20:80 to about 50:50, about 50:50 to about 70:30, or about 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, or about 70:30, or any combination or range encompassing any of the above values. In another embodiment, when the thermoplastic toughening agent is or comprises a thermoplastic polyurethane, the thermoplastic polyurethane can be a polyester polyurethane, a polyether polyurethane, or any combination thereof. In yet another embodiment, when the thermoplastic toughening agent is or comprises an acrylic elastomer, the acrylic elastomer can be an ethylene-acrylic terpolymer. In one embodiment, when the thermoplastic toughening agent is or comprises a chlorinated rubber, the chlorinated rubber can be polychloroprene, a chloropolyethylene copolymer, or any combination thereof.In one aspect, and without wishing to be bound by theory, it is believed that, unlike the inventive compositions herein, some SEBS polymers do not encapsulate or partially encapsulate brominated flame retardants upon blending, and not all blend systems comprising SEBS and brominated flame retardants satisfy the system disclosed herein.

[0019] In any of the above aspects, the flame retardant plastic composition can further include a compatibilizer. In one aspect, the compatibilizer can be maleic anhydride grafted polypropylene.

[0020] In one embodiment, the flame retardant plastic composition can comprise about 65% to about 85% by weight of the polymer component, about 65% to about 75% by weight of the polymer component, about 70% to about 80% by weight of the polymer component, or about 65, 70, 75, 80, or about 85% by weight of the polymer component, or any combination of the above values ​​or ranges of the polymer component encompassing any of the above values. In one embodiment, the flame retardant plastic composition can comprise about 5% to about 35% by weight of the brominated flame retardant, about 15% to about 25% by weight of the brominated flame retardant, about 20% to about 30% by weight of the brominated flame retardant, or about 5, 10, 15, 20, 25, 30, or about 35% by weight of the brominated flame retardant, or any combination of the above values ​​or ranges of the brominated flame retardant. The flame retardant may comprise a brominated flame retardant having a content of 100 ppm or less and a range of values ​​inclusive.

[0021] In some embodiments, the flame-retardant plastic compositions disclosed herein can also include a synergist. In further embodiments, the synergist can be antimony trioxide (herein SbO or ATO) or other 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 SbO or other synergist, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt. % of SbO or other synergist, or a combination of the above values ​​or a range of the synergist encompassing any of the above values.

[0022] In yet another embodiment, the flame retardant plastic composition can include about 4% to about 8% by weight of the thermoplastic toughening agent, about 4% to about 6% by weight of the thermoplastic toughening agent, about 6% to about 8% by weight of the thermoplastic toughening agent, or about 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or about 8% by weight of the thermoplastic toughening agent, or any combination or range of the thermoplastic toughening agent encompassing any of the above values. In yet another embodiment, the flame retardant plastic composition can include from about 0 wt % to about 2 wt % of the compatibilizer, from about 0.25 wt % to about 0.5 wt % of the compatibilizer, from about 0.5 wt % to about 1 wt % of the compatibilizer, or about 0, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, or about 2 wt % of the compatibilizer, or any combination or range of the compatibilizer of the foregoing values. In any of the above embodiments, the weight percent is based on the total weight of the polymeric component, the brominated flame retardant, the thermoplastic toughening agent, and, if present, the compatibilizer.

[0023] In another embodiment, the flame retardant plastic composition can further include a filler such as talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH), AlO(OH), Mg(OH), kaolinite, wollastonite, mica, glass beads, or any combination thereof.

[0024] In one embodiment, the flame retardant plastic composition has a melt flow rate of about 7.5 to about 20 g / 10 min, or a melt flow rate of about 7.5, 10, 12.5, 15, 17.5, or about 20 g / 10 min, or a melt flow rate of any combination of the foregoing values, or a melt flow rate range encompassing any of the foregoing values.

[0025] Also disclosed herein is an article comprising or made from the flame-retardant plastic composition disclosed herein. In one embodiment, the article has a flame retardant resistance of about 4 to about 7 kJ / m at 25°C. 2 , about 4 to about 6 kJ / m 2 , about 6~7kJ / m 2 Izod impact strength of about 4, 4.5, 5, 5.5, 6, 6.5, or about 7 kJ / m 2 or any combination of the foregoing values, or a range including any of the foregoing values. In a further embodiment, the article has an Izod impact strength of from about 6.5 to about 10.5 kJ / m at −37° C. 2 , about 6.5~8.5kJ / m 2 , about 7.5~9.5kJ / m 2 or about 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, or about 10.5 kJ / m 2 In yet another embodiment, the article can have an Izod impact strength of from about 45% to about 600%, from about 45% to about 100%, from about 100% to about 300%, from about 300% to about 600%, or an elongation at break of about 45, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, or about 600%, or an elongation at break of any combination of the above values ​​or a range including any of the above values.

[0026] In one embodiment, the article has a compressibility of about 0.9 MPa m at 25°C. -1 / 2 ~Approx. 1.2MPa m -1 / 2 , about 0.9~1.1MPa m -1 / 2 , about 1.0~1.2MPa m -1 / 2 Critical stress intensity factors of 0.9, 1.0, 1.1, or 1.2 MPa m -1 / 2 The article may have a critical stress intensity factor of about 15 MPa to about 30 MPa, about 15 to about 20 MPa, about 20 to about 30 MPa, or a tensile strength of about 15, 20, 25, or about 30 MPa, or a combination of any of the above values ​​or a range including any of the above values. In one embodiment, the article has a tensile strength of about 1700 MPa to about 4300 MPa, about 1700 MPa to about 2500 MPa, about 2500 MPa to about 3500 MPa, about 3500 MPa to about 4300 MPa, a tensile modulus of 1700, 2000, 2500, 3000, 3500, 4000, or about 4300 MPa, or a combination of any of the above values ​​or a range including any of the above values. In one embodiment, the article has a notched Izod impact strength of about 80 J / m to about 1100 J / m, about 100 to about 400 J / m, about 400 to about 800 J / m, or about 800 to about 1100 J / m, or a notched Izod impact strength of about 80, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, or about 1100 J / m, or any combination of the above values ​​or a range including any of the above values. In any of the above embodiments, the article can have a flammability rating of V0 according to the UL94 test method.

[0027] Also disclosed herein are methods for making the disclosed flame-retardant plastic compositions. In certain embodiments, the methods include at least the steps of: (a) combining a polymer component, a brominated flame retardant, and a thermoplastic toughening agent to form a precursor mixture; and (b) extruding the precursor mixture at an elevated temperature.

[0028] In a further embodiment, steps (a) and (b) can be carried out by any method known in the art. In one embodiment, steps (a) and / or (b) are carried out in a twin-screw extruder. In a further embodiment, the elevated temperature can be about 160°C to about 230°C, about 190°C to about 210°C, about 210°C to about 230°C for polyolefins or polystyrenes, or about 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, or about 230°C, or any combination or range of the foregoing values. The processing temperature can be about 160°C to about 345°C for PPA (polyphthalamide or high-temperature nylon). In one embodiment, the twin-screw extruder has a speed of about 60 rpm to 500 rpm. In another embodiment, the design and operation of the twin screw extruder encompasses methods and parameters known to those skilled in the art.

[0029] In some embodiments, the flame retardant plastic composition can be prepared by mixing the polymeric components, the brominated flame retardant, and the thermoplastic toughening agent in a double arm mixer.

[0030] In a further aspect, the method includes at least the steps of: (a) mixing a polymer component with a brominated flame retardant to prepare an initial composition known to those skilled in the art as a masterbatch; (b) mixing the masterbatch with a thermoplastic toughening agent to prepare a second, final mixture; and (c) extruding the final mixture at an elevated temperature.

[0031] In a further aspect, steps (a), (b), and (c) can be carried out by any method known in the art. Step (c) and / or step (c) are carried out in a twin-screw extruder. In further embodiments, the elevated temperature can be about 160°C to about 230°C, about 190°C to about 210°C, about 210°C 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 or range of the foregoing values. In one embodiment, the twin-screw extruder has a speed of about 60 rpm. In another embodiment, the design and operation of the twin-screw extruder encompasses methods and parameters known to those skilled in the art.

[0032] In any of the above methods, if a synergist, such as antimony trioxide, is used, the synergist can be added at any stage during the mixing process.

[0033] Those skilled in the art of the compositions and methods of the present disclosure will recognize many modifications and other aspects of the present disclosure with the aid of the teachings set forth in the foregoing description and the associated drawings. It is therefore to be understood that the present disclosure is not limited to the particular aspects disclosed, and 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 modifications of the aspects described herein. Such variations and modifications are encompassed within the teachings of the present disclosure and are intended to be encompassed within the scope of the claims.

[0034] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0035] As will be apparent to those skilled in the art from 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.

[0036] Any recited method can be carried out in the order of events recited, or in any other order that is logically possible. Unless expressly specified otherwise, it is in no way intended that any method or embodiment set forth herein be construed as requiring that its steps be performed in a particular order. Thus, unless a method claim specifically specifies, either in the claim or in the description, that the steps be limited to a particular order, no order is intended to be implied in any way. This holds true against all possible, unexpressed, grounds for interpretation, such as logical questions regarding the order of steps or operational flow, apparent meanings derived from grammatical construction or punctuation, or the number or type of embodiments described herein.

[0037] Although aspects of the present disclosure may be described and claimed in particular statutory categories (e.g., system statutory categories), this is for convenience only, and it will be apparent to those skilled in the art that each aspect of the present disclosure may be described and claimed in any statutory category.

[0038] It should be understood that the terms used herein are merely for the purpose of describing particular embodiments 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. It should also be understood that terms as defined in commonly used dictionaries should be interpreted as having a meaning consistent with such meaning in the context of this specification and related art, and should not be construed as being expressly defined herein. Unless otherwise specified, it should not be interpreted in an idealized or overly formal sense.

[0039] Prior to describing various aspects of this disclosure, the following definitions are provided. Unless otherwise indicated, it is preferred to use the following definitions. Additional terms may be defined elsewhere in this disclosure.

[0040] definition As used herein, "comprising" is to be interpreted as specifying the presence of the stated features, elements, steps, or components, but does not exclude the presence or addition of one or more features, elements, steps, or components, or groups thereof. Also, the terms "by," "comprising," "comprises," "comprised of," "including," "includes," "including," "involve," "involved," and "such as" are used in their open, non-limiting sense, and they can be used interchangeably. Furthermore, the term "comprising" is intended to include examples and embodiments 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."

[0041] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to "a polymer," "a brominated flame retardant," or "an article" includes, without limitation, mixtures or combinations of two or more such polymers, brominated flame retardants, or articles.

[0042] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in range format. It should be further understood that the endpoints of each of such ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It should also be understood that, while a number of values ​​are disclosed herein, each value is also disclosed herein as "about" that particular value, in addition to the value itself. For example, if a value of "10" is disclosed, "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 use of the antecedent "about," it should be understood that the particular value constitutes a further aspect. For example, if a value of "about 10" is disclosed, "10" is also disclosed.

[0043] 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, a phrase "from x to y" includes a range from "x" to "y," as well as a range from greater than "x" to less than "y." Ranges can also be expressed as upper limits, such as "about x, y, z, or less," which should be understood to include the ranges "less than x," "less than y," and "less than z," as well as the specific ranges of "about x," "about y," and "about z." Similarly, a phrase "about x, y, z, or greater" includes "about x," "about y," and "less than z." The specific ranges "greater than x," "greater than y," and "greater than z" should be understood to include the ranges "greater than x," "greater than y," and "greater than z." Furthermore, the phrase "about x to y" (where x and y are numbers) encompasses "about x to about y."

[0044] It will be appreciated that such range formats are used for convenience and brevity and should be interpreted flexibly to include not only the numerical values ​​explicitly stated as range boundaries but also all individual numerical values ​​and subranges encompassed therein, and each such value and subrange should be deemed to be expressly set forth. For example, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly stated value of about 0.1% to about 5%, but also individual values ​​within the specified range (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).

[0045] As used herein, the terms "about," "approximately," "at or about," and "substantially" mean that such amount or value may be exactly that value or a value that will produce an equivalent result or effect as claimed or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximate and / or increased or decreased as necessary to produce an equivalent result or effect, and may reflect tolerances, conversion factors, rounding, measurement error, and the like, as well as other factors known to those of ordinary skill in the art. In some situations, a value that will produce an equivalent result or effect may not be reasonably determined. In such cases, as commonly understood, "about" and "at or about," as used herein, mean a variation of ±10% of the stated value unless otherwise indicated or suggested. In general, a quantity, size, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "at or about," regardless of whether it is expressly stated otherwise. When "about," "approximately," or "in or about" is used before a quantitative value, that parameter also includes the particular quantitative value itself, unless otherwise specifically stated.

[0046] As used herein, the term "effective amount" refers to an amount sufficient to modify the physical properties of a composition or material as desired. For example, an "effective amount" of a thermoplastic toughening agent refers to an amount sufficient to provide the desired improvement in the property controlled by the compounding ingredients, e.g., an amount sufficient to encapsulate and / or compatibilize the brominated flame retardant in the polymer phase at the desired level. The specific wt% level in the composition required as an effective amount depends on various factors, including the amount and type of polymer component, the amount and type of thermoplastic toughening agent, the amount and type of brominated flame retardant, and the end use of the article manufactured using the composition.

[0047] As used herein, the terms "optional" or "optionally" mean that the event or circumstance described thereafter may or may not be present, and that the description encompasses both the presence and absence of the event or circumstance in question.

[0048] A "thermoplastic" polymer becomes plastic, flexible, or moldable when heated and resolidifies when cooled. The temperature at which a thermoplastic polymer softens can vary depending on the composition of the polymer. Thermoplastic polymers do not exhibit a change in chemical properties or composition after heating and resolidification. Thermoplastic compositions can be processed using a variety of methods, including extrusion, injection molding, thermoforming, etc.

[0049] As used herein, an "elastomer" is a polymer that exhibits elastic or rubber-like properties, being able to recover its original shape after being stretched or subjected to another stress. Elastic polymers have a molecular structure that is disorganized and amorphous at rest. A "thermoplastic elastomer" is a thermoplastic polymer that also possesses rubber-like elasticity.

[0050] The "UL94 test method" is a test method developed by Underwriters Laboratories (UL) that is intended to provide a preliminary indication of whether a plastic is acceptable for use as part of an article with regard to flammability. For example, to achieve a V-0 flammability rating, the article must stop burning within 10 seconds after applying a flame to a test bar twice for 10 seconds each. Flaming drops may not be present.

[0051] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (ie, 1 atmosphere).

[0052] Having described aspects of the present disclosure above, the following examples generally describe some further aspects of the disclosure. Aspects of the present disclosure will be described in conjunction with the following examples and corresponding descriptions and figures, but it is not intended to limit aspects of the present disclosure to such descriptions. Rather, it is intended to cover all alternatives, modifications, and equivalents that fall within the spirit and scope of the present disclosure. [Example]

[0053] The following examples are presented to provide those of ordinary skill in the art with a full disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed in this disclosure are made and evaluated, and are intended as merely 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, temperatures, etc.), but some error and deviation should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is °C or is room temperature, and pressure is at or near atmospheric.

[0054] Example 1: Polypropylene Systems, Materials, and Models Materials and model systems PP (Grade name: Profax 6523, Isotactic index ≥ 94, M w: 342,000 g / mol, PDI: 9.4) was obtained from LyondellBassel, and BPS (intermediate M w , research grade) was provided by Albemarle. Used rubber (grade name: SEBS G1652, styrene content: 30 wt%, Mw: 85,000 g / mol, PDI: 1.2) was obtained from Kraton.

[0055] A total of six different model systems were prepared, as shown in Table 1. Regarding some notes describing specific model systems, PP / BPS[L] refers to a binary system in which large BPS particles are dispersed in PP, PP / BPS / SEBS[SD] refers to a ternary system in which BPS and SEBS are separately dispersed in PP, PP / BPS[S] refers to a binary system in which small BPS particles are dispersed in PP, and PP / BPS / SEBS[CS] refers to a ternary system in which BPS and SEBS in PP have a core-shell structure. These are based on the morphological observations shown in Figures 4A–4D, respectively. As a control system, PP was similarly extruded and molded into specimens, which had the same thermal history as the other model systems. It is known that approximately 18–19 wt% total bromine is required to achieve a UL94V-0 grade for polyolefins. Therefore, model systems were designed to have this total bromine weight percentage. The amount of SEBS was arbitrarily chosen to be 4 wt % to maximize encapsulation of BPS and minimize modulus loss. [Table 1]

[0056] Extrusion, injection molding, and compression molding After manually mixing the PP, BPS pellets, and rubber powder in a transparent zipper bag, all model systems were extruded in a twin-screw extruder (ThermoFisher Process 11, L / D = 40) with one feeder (two screws). The total feed weight was 2 kg, and the amount recovered from the extruder was 1.5 kg. The compositions are shown in Table 1. The extrusion temperatures indicate that the temperatures in all barrel zones (die and zones 1-7) were 190 °C or 230 °C, depending on the composition in Table 1. The twin screw speed of the extruder and the single screw speed of the feeder were 60 RPM and 5 RPM, respectively. After extrusion, the strands were cooled in a water bath and manually chopped. The resulting chopped pellets were injection molded (Thermo Scientific HAAKE MiniJet Pro) or compression molded (PHI Model PW-22). The injection barrel was set to the same temperature as the extrusion temperature for each model system. The mold temperature and injection pressure (hold pressure) were 60°C and 670 bar, respectively, during a 15-second cooling period. For the SN3PB and DN4PB test samples, each model system was compression molded from a mold with a cavity size of 127 mm x 60 mm x 6.4 mm at the same temperature as its extrusion temperature under a pressure of 6 MPa, and then quenched in a water bath.

[0057] Izod impact strength Under the processing conditions described in Section 2.2, rectangular bar specimens (63.5 mm × 12.7 mm × 3.2 mm) were prepared in an injection molding machine, and then a notch (radius: 250 μm) was machined. Impact tests were performed in accordance with ASTM D256 using a pendulum impact tester (Tinius Olson Model 66, impact velocity: 2.9 m / s) at room temperature (25 °C). The thickness of each specimen and the notch depth were carefully measured with a micrometer (Mitutyo Model 543, resolution: 1 μm). Five specimens for each model system were measured and averaged.

[0058] Tensile strength Dog-bone type tensile test specimens (ASTM D638, Type IV) were prepared under the same injection molding conditions as the Izod impact test specimens. Tensile tests were performed according to ASTM D638 using a tensile tester (Instron Model 5567, load cell: 5 kN) at room temperature (25 The test was carried out at a temperature of 100°C and a crosshead speed of 5 mm / min. Three specimens were measured and averaged for modulus of elasticity, yield strength, and elongation at break.

[0059] Critical energy release rate (G 1c ) As described in Section 2.1, eight rectangular specimens (127 mm × 12.7 mm × 6.4 mm) with a central linear crack were machined from compression-molded plates for each model system. The linear crack consisted of a machined portion and a sharp crack portion. The sharp crack was generated using a new razor blade. To generate the crack, the razor blade was slid across the scratch tester under a linearly increasing normal load (1–50 N). The length of the razor blade was the same for all specimens (600 ± 50 μm). The machined notch length was adjusted separately so that each specimen had a different initial total crack length within the range of 0.3 ≤ a / W ≤ 0.7. The test setup consisted of a single-sided notched three-point bending (SN3PB) test at an impact velocity of 2.9 m / s. Detailed information on the specimen and test geometry and the formation of sharp cracks is presented in Figures 1A-2A.

[0060] The critical energy release rate (G) in Mode I is calculated using the following equation: Ic ) was sought.

[0061] By defining compliance (deflection coefficient) and energy release rate,

number

[0062] By combining Equation 1 and Equation 2,

number

number

[0063] When the pendulum head hits the SN3PB specimen, the total energy U t includes an additional energy term U0, which does not contribute to the energy dissipation associated with the formation of a new surface due to fracture. U0 includes the kinetic energy of the fractured specimen as it flies off, the frictional energy between the specimen and the jig, and the acoustic energy. U0 was calculated by floating the fractured specimen on the jig and impacting it again, as shown in Figure 1D. The additional frictional energy generated between the fractured specimen and the auxiliary rod was assumed to be negligible.

[0064] Compliance functions for loading points according to Guinea, independent of any span length, to obtain accurate calibrated energy coefficients in generalized SN3PB configuration conditions was applied.

[0065] The derivative of the compliance function is required to obtain the energy calibration factor. The differential form (dC / dα) of the energy calibration factor (φ) was calculated from the compliance function in Table 2 using Wolfram Mathematica software. The initial total crack length of each specimen was measured using a portable moving microscope (Dinolite AM311S), as shown in Figure 2B. For each model system, the fracture energy values ​​(U) of the eight specimens were plotted against their normalized area (BWφ). The slope of the plot corresponds to the critical energy release rate (G Ic ) [Table 2]

[0066] Qualitative reinforcement mechanism testing The preparation of specimens for double-notched four-point bend (DN4PB) tests was the same as for SN3PB. One difference is that the specimens have two sharp cracks, as shown in Figure 3A. Nearly identical, but not completely identical, cracks were created using an instrumented scratch tester. During the impact fracture process of four-point bending, both cracks develop similar damage propagation zones (although one propagates while the other stops). As shown in Figure 3B, a foam damper (3 mm thick) was used to minimize asymmetric impact from the two contact points between the impact head and the specimen. This technique is useful for observing pre-critical fracture features, which are a phenomenon that occurs just before crack propagation. Fractography was first performed using an optical microscope (OM), followed by petrographic thin sectioning to observe the gross condition of the damaged area, and then transmission electron microscopy (TEM) to observe microscopic damage (or strengthening) features. Mid-plane sections were prepared using a Bühler ISOMET1000 diamond saw. One side of the mid-section was embedded in epoxy, mounted on a glass slide, and carefully polished to a maximum thickness of 80 μm for optical microscopy (Figure 3D). The other side was embedded in an epoxy block for TEM observation.

[0067] optical microscopy The imaging process in transmission mode under bright field (TOM) and crossed polarizers (POM) was carried out on the polished sample. The polished sample was then analyzed according to the petrographic method, as shown in Figure 3D. After preparation, the specimens were mounted on glass slides under an optical microscope (Olympus BX60) without any additional filters.

[0068] Staining process and TEM microscopy To distinguish the different phases, a pre-staining method was applied. The styrene phase of SEBS rubber is known to be stained by RuO4. The embedded block faces were trimmed using a diamond knife at -60 °C and cryo-polished to prevent smearing. The cryo-polished blocks were then stained with the vapor phase of a 2% RuO4 aqueous solution for 4 h at ambient temperature. The staining solution was prepared using 5.25% aqueous sodium hypochlorite and ruthenium(III) chloride hydrate (RuCl3 × H2O) in a glass jar with a screw cap. After staining, the embedded blocks were placed in deionized water overnight, after which they were sectioned to dissipate residual RuO4 from the samples. The stained block faces were thin-cut to a thickness of 120 nm using a diamond knife with a water boat, and several thin sections were transferred to copper grids in a microtome (Leica EM UC7 Ultramicrotome) at ambient temperature. TEM imaging was performed using a JEOL 1200X microscope under an electron beam voltage of 100 keV. For each model system, the BPS particle size was determined by averaging three different TEM images.

[0069] Surface energy measurement Surface energy analysis of BPS was performed using an iGC surface energy analyzer, SEA (Surface Measurement Systems), and the data values ​​were analyzed using an SEA analysis software package. The measurement process is briefly summarized here, but detailed methods can be found in several references. Approximately 150 mg of BPS powder sample was packed into individual silanized glass columns. The total surface area of ​​the powder sample was measured in nm using probe molecules, and then different amounts of the probe molecules were injected into the column. The normalized surface area is expressed in units of n / nm. In the next step, a different series of probe molecules were injected into the column after regeneration with helium gas, and then the retention time was measured for each experiment. The retention time of the probe molecules interacting with the powder material in the iGC column was measured and converted to net retention volume using a James-Martin correction factor. The Gibbs free energy of adsorption was calculated by substituting the net retention volume into Henry's law, which relates the free energy of adsorption to the work of adhesion to the surface of the powder material. More detailed information is provided in the following literature. Nonpolar probe molecules (heptane, octane, nonane, and decane) and polar probe molecules (dichloromethane, ethyl acetate, acetone, acrylonitrile, and ethanol) were applied to measure the dispersive surface energy (γ d ) and polar surface energy (γ p ) were determined. All experiments were performed at 30°C. Methane gas was used for dead volume correction. The Dorris-Gray and Good-van Oss-Chaudhury model methods were employed to determine the dispersion and polar terms of the surface energy. The dispersion and polar terms of the surface energy of the BPS obtained are shown in Table 3. γ10, γ50, and γ90 refer to the values ​​corresponding to the area under the surface energy plot along the coverage, calculated using an exponential decay function. Here, the distribution of surface energy is due to defects and imperfections on the surface. The γ50 value is widely adopted as a representative value of the surface energy. The value of -dγ / dT for BPS is calculated based on a linear approximation from the density value plot using Equation 6.

number

[0070] Measured in a pycnometer using silicone oil at temperatures of 25, 40, 50, 60, and 70°C The density values ​​of BPS were 2.22, 2.20, 2.18, 2.17, and 2.16, respectively. [Table 3]

[0071] Example 2: Polypropylene System, Results and Discussion Morphological Analysis Glass transition (T g ) is known to be in the range of 163-182°C. Both the 190°C and 230°C processing temperatures are g The first clear observation, shown in Figures 4A and 4C, is the size change of BPS particles at different temperatures in a PP / BPS binary system. At higher processing temperatures, the degree of mixing is observed to be easier due to the decrease in BPS viscosity, which can lead to better dispersion kinetically. This observation confirms that PP and BPS are immiscible polymer blends. Miscible polymers with BPS are rare.

[0072] Ternary polymer blends of PP, BPS, and SEBS not only differ in BPS particle size, but also exhibit significant morphological differences, as shown in Figures 4B and 4D. At a processing temperature of 190°C, BPS and SEBS are dispersed separately. Meanwhile, BPS particles are encapsulated by the SEBS rubber, in addition to the good dispersion of smaller BPS particles. In the RuO4-stained sample, the dark phase is SEBS due to the higher electron density of ruthenium relative to bromine. To further investigate the underlying reasons for the morphological differences, thermodynamic spreading theory was applied. Since Hobbs proposed the modified Harkins equation, morphological predictions from this model have been in good agreement with experimental observations for ternary polymer blends. The total surface energies of selected materials, as well as their dispersion and polar terms, for BPS, PP, and SEBS are shown in Table 3 and Figure 4A. Each interfacial energy

number

number

[0073] Expansion Factor

number

[0074] The dispersive and polar components of the surface energy of BPS are shown in Table 3 and Figures 2A-2B. γ10, γ50, and γ90 represent values ​​corresponding to the area under the surface energy plot by using an exponential decay function. The distribution of surface energy depending on the surface coverage is caused by imperfections on the BPS surface, such as defects. γ50 is selected as a representative value for the expansion coefficient formula for morphology estimation. The expansion coefficient S BPS·SEBS maintains a negative value over the entire temperature range. On the other hand, the expansion coefficient S SEBS·BPS becomes positive above a temperature of 220 °C, which means that the core-shell morphology is thermodynamically favored. This assumption is consistent with the results of TEM observations.

[0075] Izod impact and tensile behavior Izod impact strength is an easy and rapid screening tool for comparing the relative ranking of systems with superior impact properties. The PP / BPS / SEBS[SD] system shows no improvement over PP / BPS[S]. One possible scenario is that crack propagation is dominated by large particles, either through weak interfaces or by splitting hard particles. On the other hand, PP / BPS / SEBS[CS] shows a significant improvement over the other three model systems containing BPS, with its impact strength approaching that of PP / SEBS. The rubber-coated BPS particles appear to act as a toughening agent.

[0076] In the tensile behavior, the PP / BPS[L] and PP / BPS / SEBS[SD] specimens containing large amounts of BPS began to fracture immediately after yielding. PP / BPS[S] and PP / BPS / SEBS[CS] showed the phenomenon of necking propagation after yielding, while PP / BPS[L] and PP / BPS / SEBS[SD] did not exhibit necking. Interestingly, even though the same amount of SEBS was compounded into PP / BPS / SEBS[SD] and PP / BPS / SEBS[CS], their moduli were quite different. PP / BPS / SEBS[CS] had a modulus even lower than PP and comparable to that of PP / SEBS. Therefore, under this far-field uniaxial stress condition, the matrix is ​​primarily affected at the interface with SEBS rather than BPS, which is indirect evidence that the rubber-encapsulated BPS particles behave like rubber particles. Based on their analytical studies, Matonis et al. confirmed that when the thickness of the coated rubber exceeded approximately 4% of the radius of the hard particle, the modulus approached that of a two-component polymer system containing only rubber. [Table 4]

[0077] Critical energy release rate (G 1c ) and reinforcement mechanisms Izod and Charpy impact strengths have limitations due to geometrical dependencies such as notch radius and length, span length, and specimen thickness. Therefore, much effort has been devoted to obtaining geometrically independent fracture toughness parameters under impact conditions. The critical energy release rate is an intrinsic fracture toughness value based on linear elastic fracture mechanics [LEFM]. Large-particle-dominated systems (PP / BPS[L] and PP / BPS / SEBS[SD]) exhibit lower fracture toughness than the PP system. This means that these large-particle systems exhibit lower resistance to the propagation of sharp crack tips, resulting in materials behaving more brittle than the matrix polymer. In Figures 8A and 8C, the crack penetrates the BPS particles, with no crack suppression mechanism. This is typical of brittle fracture in systems incorporating hard particles. The PP / BPS[S] system also exhibits a significant decrease in fracture toughness in Figure 7C. Crazing (a typical damage behavior in front of the crack tip in thermoplastic materials) is more suppressed than in the PP case, as shown in Figures 9A and 11A. However, PP / BPS / SEBS[CS] showed significantly improved fracture toughness. This may be due to shear banding caused by the formation of large crazes. The relaxation of triaxial stress constraints due to volume expansion initiates shear yielding. Here, large crazes are the main cause of volume expansion. To clearly investigate the microtoughening mechanism of PP / BPS / SEBS[CS], TEM was performed on another portion of the arrested crack after the DN4PB test (Figure 10). Direct evidence was revealed that large crazes were initiated and stabilized from the rubber-coated BPS particles. Further stress accumulation accompanied by volume expansion led to shear banding. Therefore, our proposed mechanism is craze formation / shear banding, as shown in Figure 12. Although rubber-encapsulated BPS certainly acts as a toughening agent, its toughening mechanism is slightly different, as shown in Figures 11C-11D. Cavitation in SEBS rubber is preceded by volume expansion accompanied by craze formation, followed by a shear band formation mechanism. A similar mechanism can be found in Ref.

[0078] conclusion By carefully selecting processing conditions, we successfully prepared BPS particles encapsulated with SEBS rubber. The morphological differences between the core-shell structure and the isolated dispersed structure in ternary polymer blends of PP, BPS, and SEBS were consistent with theoretical calculations based on thermodynamic spreading theory. SEBS rubber encapsulated the hard BPS particles and emulsified the BPS dispersion as a compatibilizer, significantly improving fracture toughness. Therefore, the concept that rubber-coated BPS functions as a toughening agent was verified. The toughening mechanism involves the promotion of craze initiation / shear band formation. As a result, the rubber-coated BPS acted as both a toughening agent and a compatibilizer.

[0079] Example 3: LLDPE Systems, Materials, and Methods material LLDPE (grade: Petrothene GA564189) was purchased from LyondellBasell Industries. BPS was supplied by Albemarle Corporation. SEBS rubber (grade: Kraton FG1901, maleic anhydride grafted SEBS) was kindly provided by Kraton Corporation. All were used in the form of pellets as received.

[0080] Sample preparation The polymer blend compositions and processing conditions are listed in Table 6. The weight ratio of LLDPE / BPS is fixed at 75:25, and different amounts of SEBS rubber are added as a compatibilizer. For a particular composition, all pellets are mixed together in one step in a twin-shaft Haake mixer (Rheocord Each composition was mixed for 7 minutes at a constant temperature with a screw speed fixed at 60 rpm. [Table 5]

[0081] The mixed resin was then injection molded into tensile bars (ASTM D638, V-shaped) and rectangular bars (63.5 mm × 12.7 mm × 3.2 mm) for mechanical testing. Injection molding was performed using a Haake MiniJet Pro Piston Injection Molder (Thermo Fisher Scientific Inc.) at a cylinder temperature of 190 °C, a mold temperature of 60 °C, and an injection pressure of 680 bar.

[0082] Characterization Morphology Microscale morphology was observed using an Olympus BX60 optical microscope (OM). Samples (5 mg) were placed between two glass slides and then hot-pressed at 190 °C to form thin films for OM observation.

[0083] Transmission electron microscope (TEM) images for nanoscale morphology observation were acquired using a JEOL JEM-1200 operating at 100 keV. Ultrathin sections with a thickness of 100 nm were prepared using a Reichert-Jung Ultracut E ultramicrotome equipped with a diamond knife at cryogenic temperatures.

[0084] Rheology Rheological measurements were performed using a TA Instruments ARES-G2 rheometer. Parallel plates with a diameter of 25 mm were used. Strain sweep measurements were first performed to determine the linear viscoelastic region, followed by frequency sweep measurements from 100 rad / s to 0.1 rad / s at 230 °C under nitrogen gas protection.

[0085] Mechanical Inspection Tensile properties were measured using an Instron universal testing machine. Tensile test bars (ASTM D638, Type V) were stretched uniaxially at a crosshead speed of 25.4 mm / min, and the change in gauge length was monitored with an extensometer. Engineering stress-engineering strain plots were used to determine modulus, yield strength, and elongation at break. Secant modulus at 1% strain was measured. At least five specimens were tested for each system, and the average value was recorded.

[0086] Notched Izod impact tests were performed at -37°C using a Tinius Olsen plastic impact tester according to ASTM D256. A 22.6 J pendulum hammer was used. V-notched specimens (63.5 mm x 12.7 mm x 3.2 mm) were first preconditioned at -37°C for 1 hour in an environmental chamber (Standard Environment Systems, Inc.) attached to the impact tester. Upon opening the environmental chamber, the specimens were immediately struck with the pendulum hammer to minimize specimen heating. The absorbed energy was used to calculate impact strength. At least five specimens were tested for each system, and the average value was recorded.

[0087] Evaluation of strengthening mechanisms Double-notch four-point bend (DN-4PB) specimens were prepared as shown in Figures 13A-13C. First, a notch was created in the specimen to a depth of 2.54 mm using a notch cutter. Two nearly identical, sharp pre-cracks were then created using a new razor blade cooled in liquid nitrogen. DN-4PB Charpy impact tests were performed at -37 °C in a pendulum impactor equipped with a double-head impactor. One pre-crack eventually fractured, while the other remained. The remaining cracks were thin-sectioned to observe the damaged area in both bright-field and cross-polarized OM, and the fracture surface was examined using a JEOL JSM-7500F field emission scanning electron microscope (SEM) operated at 5.0 kV.

[0088] Example 4: LLDPE Systems, Results, and Discussion Morphology Figure 14 shows the effect of SEBS addition and processing temperature on morphology. When LLDPE and BPS are mixed at 185°C, the particle size of the dispersed BPS phase in this non-compatibilized system can grow to 40 μm. The shape of the dispersed BPS phase appears to be irregular rather than spherical. The addition of SEBS slightly improves the dispersion of BPS, but the particle size remains large at 10-20 μm. When LLDPE and BPS are mixed at a higher temperature of 230°C, the BPS particles become uniformly dispersed with a particle size of less than 5 μm. Adding SEBS rubber When such particles are mixed at 230 °C, the dispersion is further improved, and the BPS particle size becomes too small to be detected under OM. Further morphological investigations using TEM on the well-dispersed 8 phr / 230 °C system suggest that the BPS particle size can be reduced to less than 0.5 μm (Figures 15A-15B).

[0089] The combined effect of adding SEBS rubber and selecting an appropriate processing temperature significantly improves the dispersion of BPS in LLDPE. It has been reported that the viscosity ratio can significantly affect the morphology of immiscible polymer blends. Usually, fine dispersions are obtained, and better mechanical properties can be obtained when the viscosity ratio is close to 1. When LLDPE / BPS is mixed at a typical processing temperature of LLDPE (e.g., 185°C ( <BPSのT cf When melt-blended at 230°C, BPS is not completely melted. However, when LLDPE / BPS are melt-blended at 230°C, the viscosity ratio is 2.3, approaching monotony (Table 7). This viscosity ratio of 2.3 contributes to a significant improvement in dispersion. Higher processing temperatures (>230°C) were not investigated due to LLDPE decomposition. Once the optimal processing temperature is determined, the addition of SEBS copolymer can further help improve compatibility between the LLDPE and BPS phases. This is because the SEBS copolymer contains ethylene / butylene and styrene segments, which have good affinity for the LLDPE and BPS phases, respectively. The SEBS copolymer resides at the interface between the LLDPE and BPS phases and forms a shell layer covering the dispersed BPS particles, contributing to the formation of a core-shell structure (Figures 15A-15B). [Table 6]

[0090] Rheology The effects of different processing temperatures and the different morphologies resulting from the addition of SEBS rubber on the rheological behavior were investigated. Figure 16 shows the complex viscosities of these systems as a function of angular frequency. When BPS is added to LLDPE, the viscosity increases in the low-frequency region due to the higher viscosity of BPS. Even in the poorly dispersed systems mixed at 185°C, the addition of SEBS rubber slightly increases the viscosity. This is due to a slight decrease in the particle size of BPS, resulting in a larger interfacial area in the 4 phr / 185°C and 8 phr / 185°C systems compared to the 0 phr / 185°C system. This increase in viscosity in the low-frequency region is more pronounced in the well-dispersed systems mixed at 230°C. The well-dispersed 8 phr / 230°C system exhibits the highest viscosity in the low-frequency region. This increase in viscosity resulting from compatibilization with SEBS rubber can be attributed to three reasons. One reason is the decrease in BPS droplet size, another is the narrower particle size distribution of BPS, and most importantly, the stronger interfacial interaction between the BPS particles and the LLDPE matrix phase. The rheological response is in good agreement with the morphological observations mentioned above.

[0091] The Cole-Cole plot also shows dramatically different relaxation characteristics between the low-dispersity and well-dispersed systems (Figure 17). Polymers with a single relaxation process appear as a semicircle in the Cole-Cole plot, while a second peak indicates the presence of a different relaxation mechanism. The low-dispersity 4 phr / 185°C and 8 phr / 185°C systems exhibit a similar relaxation behavior to neat LLDPE and The results show two peaks located between the characteristic relaxation peaks of the 4 phr / 185°C and 8 phr / 185°C systems. This suggests that the 4 phr / 185°C and 8 phr / 185°C systems are only partially compatibilized, with very limited compatibilization levels. On the other hand, the well-dispersed 4 phr / 230°C and 8 phr / 230°C systems show only a single semicircle, suggesting that these systems have a single relaxation mechanism due to effective compatibilization. Compared to the 4 phr / 230°C system, the 8 phr / 230°C system shows a slight shift in the relaxation peak to the right, indicating a longer relaxation time. This is likely due to greater interfacial entanglement with the addition of more SEBS rubber. These rheological measurements suggest that morphological uniformity and interfacial interactions can be significantly enhanced in well-compatibilized systems such as the 8 phr / 230°C system.

[0092] Mechanical properties Engineering stress-engineering strain plots are shown in Figure 18. The well-dispersed systems mixed at 230°C consistently exhibit higher tensile yield stress and better elongation at break than the corresponding poorly dispersed systems mixed at 185°C (Table 8). Typically, the incorporation of BPS into LLDPE leads to an increase in modulus due to the higher stiffness of BPS. However, the addition of the softer SEBS rubber phase in the LLDPE / BPS mixture gradually decreases the modulus. The modulus at 0 phr / 230°C is nearly identical to that at 0 phr / 185°C, and the normalized crystallinity of the LLDPE is approximately 23% for all systems. These facts suggest that processing at 230°C does not cause significant degradation for either polymer. Interestingly, both the 4 phr / 230°C and 8 phr / 230°C systems exhibit lower moduli than their 185°C counterparts. Since there was no significant polymer degradation or difference in crystallinity, this can be explained solely by the difference in their morphologies. In the well-dispersed 4 phr / 230°C and 8 phr / 230°C systems, the SEBS rubber enveloped the hard BPS particles, forming a core-shell structure with a BPS core and an SEBS shell, but some SEBS chains penetrated into and mixed with the BPS core phase. The modulus of the BPS core was softened by these SEBS polymer chains, resulting in a slightly lower overall modulus. It is also possible that the core-shell morphology, with SEBS surrounding the BPS, causes the SEBS-coated BPS to behave like rubber, with the contribution of the hard BPS core to stiffness masked by the soft SEBS shell, resulting in a lower overall modulus. On the other hand, in the low-dispersed 4 phr / 185°C and 8 phr / 185°C systems, a core-shell structure did not form, and most of the SEBS rubber particles remained in the LLDPE phase (Figure 21B). Thus, the hard BPS particles are not softened by the SEBS rubber, and so the poorly dispersed systems exhibit a slightly higher modulus than their well dispersed counterparts. [Table 7]

[0093] The impact resistance of test specimens in a low-temperature environment was evaluated using a notched Izod impact test at 37°C (Figure 19 and Table 8). When mixed at 185°C, the addition of SEBS rubber in the low-dispersion system did not significantly improve impact strength. However, when mixed at 230°C, the addition of SEBS rubber significantly increased the impact strength of the test specimens. Adding more SEBS rubber to these well-dispersed systems resulted in higher toughness. Of these, the 8 phr / 230°C system had an impact strength of 10.33 kJ / m 2 This shows an impact strength of approximately four times that of the non-compatibilized system at 0 phr / 230°C.

[0094] Research into fracture mechanisms To aid in understanding the strengthening mechanism, DN-4PB Charpy impact tests were conducted. Two nearly identical precracks grow with equal probability when the specimen is impacted. One of these precracks eventually undergoes damage and fracture, while the other remains and continues to grow without fracture. Because crack propagation also occurs in front of the remaining precrack, observation of the damage region ahead of the crack tip is extremely useful for understanding the strengthening mechanism of these systems. Figures 20A–20D show the damage region ahead of the crack tip for the 8 phr / 185°C and 8 phr / 230°C systems, observed under both bright field and cross-polarized light. In the 8 phr / 185°C system, the crack propagates brittlely, directly penetrating the large BPS particles. These large agglomerates of BPS are defects through which the crack easily propagates, resulting in little energy absorption. However, in the well-dispersed 8 phr / 230°C system, large-scale craze formation was observed under bright field OM. Such strong craze formation is beneficial for energy absorption and contributes to the much higher impact strength of the 8 phr / 230°C system. Furthermore, under cross-polarized light, birefringent regions are observed in the damaged area of ​​the 8 phr / 230°C system, but not in the 8 phr / 185°C system. This indicates that shear band formation occurs during crack propagation. Shear band formation can be caused by cavitation in the core-shell rubber.

[0095] In addition to observing the damaged region ahead of the crack tip, fractographic analysis can also provide useful information about the toughening mechanism. Figures 21A–21D show the fracture surfaces of the 8 phr / 185°C and 8 phr / 230°C systems observed under SEM. Large BPS particles fractured brittlely in the 8 phr / 185°C system, consistent with the observation in Figure 21B. Peeling of BPS particles from the LLDPE matrix was also observed, indicating poor adhesion between the BPS and LLDPE phases in the poorly dispersed 8 phr / 185°C system. Furthermore, numerous small spherical particles were present in the LLDPE matrix phase and had peeled off from the LLDPE phase. These spherical particles may be SEBS rubber. Such SEBS rubber may have dispersed in the LLDPE phase rather than surrounding the BPS particles due to insufficient melt mixing at 185°C. However, in the well-dispersed 8 phr / 230°C system, small BPS particles coated with SEBS rubber were uniformly dispersed. More importantly, these particles are tightly embedded within the LLDPE matrix, demonstrating strong interfacial adhesion to LLDPE, consistent with previous rheological findings.

[0096] In this study, we investigated the morphological, interfacial, and mechanical properties of LLDPE / BPS blends compatibilized and reinforced with SEBS rubber. When melt-mixed at an appropriate processing temperature (230°C), the Izod impact strength of LLDPE / BPS / SEBS blends (75 / 25 / 8 by weight) at -37°C can be improved by nearly three times compared to the uncompatibilized system. The low-cost and simple process presented here has the potential to expand the range of applications for LLDPE to those requiring flame retardancy and low-temperature impact resistance.

[0097] conclusion The objective of this study is to harmonize and improve the properties of LLDPE / BPS polymer blends. The morphology and properties can be significantly affected not only by the addition of SEBS rubber as a compatibilizer, but also by the processing temperature. Melt mixing at 230°C allows the viscosity ratio to approach 1, and the addition of SEBS rubber reduces the BPS particle size to less than 0.5 μm, forming a core-shell structure. This fine morphology, along with the strong interfacial interactions characterized by rheology, contributes to a three-fold increase in Izod impact strength at -37°C. As evidenced by DN-4PB tests, craze formation and shear band formation caused by cavitation of the core-shell rubber are the two main toughening mechanisms of well-dispersed systems. Due to the ease of processing, this research will be valuable for the production of fire-resistant LLDPE. Future research will investigate the effect of different morphologies or BPS particle sizes on the flame retardancy of these systems.

[0098] Example 5: Further compositions using commercially available polymers material Flame retardant plastic compositions according to the present disclosure were prepared using the following commercially available polymers: [Table 8-1] [Table 8-2]

[0099] Experimental procedure Examples Compositions 1 through 9 (see Table 10) were extruded on a ThermoFisher Process 11 twin-screw extruder. The extrusion temperatures in Table 10 indicate that all barrel temperatures were 190°C or 230°C, depending on the composition. The extruder twin screw speed and feeder single screw speed were 60 RPM and 5 RPM, respectively. After extrusion, the strands were cooled in a water bath and manually chopped. Thermoplastic elastomer pellets The homo-PP pellets and BPS1 granules (or BPS2 powder), with or without BPS1 (or powder), are all mixed manually in a transparent plastic bag and then fed into the extruder. The total feed amount is 2 kg, and the final recovery amount after extrusion is 1.5 kg. [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18]

[0100] The compositions in Tables 11 to 13 were mixed in a Haake Rheocord (Model 40) mixer for 7 minutes to obtain blends containing EPB, BPS1, or ethylene-bis-tetrabromophthalimide. The total volume of one mixing batch was approximately 50 mL.

[0101] The order of adding each component to the mixing chamber is resin, then brominated flame retardant, then rubber, then compatibilizer. For example, in Example 1, after the homo-PP is completely melted, EBP is added for 1 minute, then hydrogenated rubber is added for 30 seconds, and then SEBS-g-MAH rubber is added for 30 seconds. The total mixing time is 7 minutes.

[0102] After 7 minutes, the chamber is opened and the sample is collected and then chopped into 5 mm x 5 mm x 2 mm pieces.

[0103] Injection molding is carried out at a barrel temperature of 190° C. and a mold temperature of 60° C. The cooling time is 10 seconds and the injection pressure is 670 bar. The molded bar dimensions are 90×12.7×3.2 mm.

[0104] The bars were machined to a size of 63.5 x 12.7 x 3.2 mm with a centrally located 45° notch 2.54 mm deep and then tested for Izod impact strength and plane strain critical stress intensity factor K1c according to ASTM D256 and ASTM D5056 at temperatures of 25°C or -37°C.

[0105] The examples of Compositions 25 to 53 in Tables 14 to 18 were first prepared using a Werner & Pfleider (Coperion) ZSK-30 twin-screw extruder (L / L) with two feeders. The raw materials were prepared by compounding in a D24 machine with a 30 mm screw diameter and barrel temperatures of 165–200°C (hopper to mold). Direct compounding means that all materials were fed at once. Pellets and granules were fed through one feeder, and premixed powder was fed through another. The extruded strands were cooled in an ice-water bath, air-dried, and pelletized. Continuous compounding means that BPS and the elastomeric polymer were extruded first, with or without filler. This first compound was fed to a second extrusion along with the matrix resin as a masterbatch. The pellets were then injection molded into test bars in a Boy 30A (35 ton) machine at a barrel temperature of 200°C, injection pressure of 10 MPa, and mold temperature of 35°C, with a 15-second cooling time.

[0106] Examples of Compositions 54 to 57 (Table 19) were extruded using a ThermoFisher Process 11 twin-screw extruder with one feeder. The extruder barrel temperature was 285–320°C from the hopper to the die. The twin-screw speed was 150 RPM, with a feed rate of 0.2 kg / h. The extruded strands were cooled in a conveyor belt and then chopped using a pelletizer. PPA pellets and BPS1 granules, with or without thermoplastic elastomer pellets (or powder), were all mixed manually in a clear plastic bag before being fed into the extruder. The extruded chopped pellets were injection molded using a ThermoFisher Minijet Pro at an injection pressure of 3,450 psi, a barrel temperature of 345°C, a die temperature of 90°C, and a cooling time of 15 seconds to obtain Izod test bars. For continuous compounding, the mixed materials were prepared as in Claim 126.

[0107] TEM observation Blocks of 3 × 3 × 10 mm were subjected to cryogenic ultramicrotoming with a diamond knife at a temperature of −120 °C to obtain TEM thin sections (100–120 nm thick) on TEM copper grids (400 mesh size).

[0108] Each thin section on a TEM copper grid was vapor stained with 0.5% aqueous ruthenium tetroxide solution for 10 minutes at ambient temperature to provide contrast between the resin, rubber, and brominated FR.

[0109] The morphology was observed on a JEOL 1200 EX or a JEOL JEM-1400 at an electron beam voltage of 100 keV or 120 keV, respectively.

[0110] Figures 22A-22Q show TEM images of the compositions in Tables 10-13, as follows: Figure 22A shows composition 1. Figure 22B shows composition 3. Figure 22C shows composition 4. Figure 22D shows composition 5. Figure 22E shows composition 7. Figure 22F shows composition 8. Figure 22G shows composition 10. Figure 22H shows composition 11. Figure 22I shows composition 12. Figure 22J shows composition 16. Figure 22K shows composition 17. Figure 22L shows composition 18. Figure 22M shows composition 20. Figure 22N shows composition 21. Figure 22O shows composition 22. Figure 22P shows composition 23. Figure 22Q shows composition 24. Figure 22R shows composition 25. Figure 22S shows composition 26. Figure 22T shows composition 31. Figure 22U shows composition 34. Figure 22V shows composition 48. Figure 22X shows composition 52. Figure 22Y shows composition 54. Figure 22Z shows composition 56.

[0111] 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 changes and modifications can be made to the above-described embodiment(s) without substantially departing from the spirit and principles of the present disclosure. It is intended that all such modifications and modifications be included herein within the scope of this disclosure and protected by the following claims.

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Claims

1. 1. A flame retardant plastic composition comprising a polymer component and a brominated flame retardant, wherein the brominated flame retardant comprises one or more particles at least partially encapsulated by a thermoplastic toughening agent.

2. 2. The flame-retardant plastic composition of claim 1, wherein the polymer component comprises polystyrene, 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), polyamide, polyester, styrenic polymer or copolymer, crosslinkable or crosslinked polyethylene (PEX or XLPE), or any combination thereof.

3. 3. The flame-retardant plastic composition of claim 2, 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), (p-phenylene / d,4'-diphenyl ether terephthalamide) copolymer, PA66 / 6, PA6T, PA9T, PA10T, PA4T, poly(m-xylylene sebacamide), poly(m-xylylene adipamide), copolymers thereof, or any combination thereof.

4. 3. The flame retardant composition of claim 2, 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.

5. 3. The flame retardant composition of claim 2, wherein the styrenic polymer or the styrenic copolymer comprises a styrene-acrylonitrile copolymer (SAN), an acrylonitrile-butadiene-styrene copolymer (ABS), or any combination thereof.

6. 3. The flame-retardant plastic composition according to claim 1, wherein the polymer component is selected from polypropylene, polystyrene, linear low-density polyethylene (LLDPE), or ethylene-1-octene copolymer.

7. 7. The flame-retardant plastic composition of any one of claims 1 to 6, wherein the brominated flame retardant comprises 1,2-bis(pentabromophenyl)ethane, brominated polystyrene, ethylene-bis-tetrabromophthalimide, decabromodiphenyl oxide, brominated polystyrene, poly(bromostyrene), polyvinyl bromide, polyvinylidene bromide, poly(2-bromoethyl methacrylate), poly(2,3-dibromopropyl methacrylate), poly(methyl-a-bromoacrylate), brominated butadiene styrene copolymer, or any combination thereof.

8. 8. The method according to claim 1, wherein the thermoplastic toughening agent comprises a thermoplastic elastomer. The flame-retardant plastic composition described above.

9. 9. The flame-retardant plastic composition of claim 1, wherein the thermoplastic toughening agent comprises a styrenic block copolymer, a thermoplastic polyurethane, a nitrile butadiene rubber, an acrylic elastomer, a copolyester elastomer, a thermoplastic polyetherester elastomer (TPEE), a thermoplastic amide ether elastomer (TAEE), a chlorinated rubber, an ionomer, a thermoplastic vulcanizate, or any combination thereof.

10. 10. The flame retardant plastic composition of claim 9, wherein the nitrile butadiene rubber comprises a hydrogenated nitrile butadiene rubber.

11. 10. The flame-retardant plastic composition of claim 9, wherein the styrenic block copolymer comprises a styrene-ethylene butylene-styrene block copolymer (SEBS), a maleic anhydride-grafted SEBS block copolymer, a styrene-ethylene propylene-styrene block copolymer (SEPS), or any combination thereof.

12. 12. The flame retardant plastic composition of claim 11, wherein the SEBS block copolymer has a styrene:ethylene+butylene ratio of from about 10:90 to about 70:

30.

13. 10. The flame retardant plastic composition of claim 9, wherein the thermoplastic polyurethane comprises a polyester polyurethane, a polyether polyurethane, or any combination thereof.

14. 10. The flame retardant plastic composition of claim 9, wherein the acrylic elastomer comprises an ethylene acrylic terpolymer.

15. 10. The flame retardant plastic composition of claim 9, wherein the chlorinated rubber comprises polychloroprene, chloropolyethylene copolymer, or any combination thereof.

16. Sb ２ O ３ The flame-retardant plastic composition according to any one of claims 1 to 15, further comprising:

17. The flame retardant plastic composition contains about 1 wt % to about 10 wt % Sb ２ O ３ 17. The flame retardant plastic composition of claim 16, comprising:

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

19. 20. The flame retardant plastic composition of claim 18, wherein the compatibilizer comprises maleic anhydride grafted polypropylene.

20. 20. The flame retardant plastic composition of claim 1, wherein the flame retardant plastic composition comprises about 65% to about 85% by weight of the polymer component, about 5% to about 35% by weight of the brominated flame retardant, about 4% to about 8% by weight of the thermoplastic toughening agent, and about 0% to about 2% by weight of the compatibilizer, based on the total weight of the polymer component, the brominated flame retardant, the thermoplastic toughening agent, and, if present, the compatibilizer.

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

22. The filler may be talc, calcium carbonate, AgO, ZnO, CaO, MnO, Al(OH) ３ , AlO(OH), Mg(OH) ２ 22. The flame retardant plastic composition of claim 21, comprising: kaolinite, wollastonite, mica, glass beads, or any combination thereof.

23. 23. The flame-retardant plastic composition of any one of claims 1 to 22, wherein the one or more particles of the brominated flame retardant comprise: (i) a plurality of particles that are individually partially encapsulated by the thermoplastic toughening agent; (ii) a plurality of particles that are individually completely encapsulated by the thermoplastic toughening agent; (iii) a plurality of clusters of two or more particles, wherein each cluster of the plurality of particles is collectively partially encapsulated by the thermoplastic toughening agent; (iv) a plurality of clusters of two or more particles, wherein each cluster of the plurality of particles is collectively completely encapsulated by the thermoplastic toughening agent; or (v) any combination thereof.

24. 24. The flame retardant plastic composition according to any one of claims 1 to 23, wherein the one or more particles at least partially encapsulated by the thermoplastic toughening agent have a core-shell structure.

25. 25. The flame retardant plastic composition according to any one of claims 24 to 25, wherein the shell layer of the core-shell structure has an average thickness of from about 5 nm to about 10 μm.

26. 26. The flame retardant plastic composition of claim 25, wherein the ratio of the average thickness of the shell layer to the average length in at least one dimension of the core layer of the core-shell structure is in the range of about 0.05:1 to about 1:1, most typically 0.05:1 to 0.25:

1.

27. The flame retardant plastic composition of any one of claims 1 to 26, wherein the flame retardant plastic composition has a melt flow rate of about 7.5 to about 20 g / 10 min.

28. An article comprising the flame retardant plastic composition of any one of claims 1 to 27.

29. 30. The article of any one of claims 28, wherein the article comprises an electronic component, an automotive component, insulation, carpet, wall covering, cable or wire coating, textile, adhesive, or any combination thereof.

30. A method for producing the flame-retardant plastic composition according to any one of claims 1 to 29, comprising: (a) mixing the polymer component, the brominated flame retardant, and the thermoplastic toughening agent to form a precursor mixture; (b) extruding the precursor mixture at an elevated temperature.

31. 31. The method of claim 30, wherein step (a), step (b), or both steps (a) and (b) are carried out in a twin-screw extruder.

32. 32. The method of claim 30 or 31, wherein the elevated temperature is from about 160°C to about 230°C.

33. 33. The method of claim 31 or 32, wherein the twin screw extruder has a speed of about 60 rpm.

34. During either step (a) or step (b), Sb ２ O ３ further comprising adding The method according to any one of claims 30 to 33.

35. 30. A method for producing the flame retardant plastic composition of any one of claims 1 to 29, comprising: mixing the polymer component, the brominated flame retardant, the thermoplastic toughening agent, and optionally Sb ２ O ３ in a double arm mixer.

36. A method for producing the flame-retardant plastic composition according to any one of claims 1 to 29, comprising: (a) mixing the polymer component and the brominated flame retardant to form a masterbatch; (b) mixing the masterbatch with the thermoplastic toughening agent to form a second mixture; (c) extruding the second mixture at an elevated temperature.

37. 37. The method of claim 36, wherein one or more of steps (a), (b), and (c) are carried out in a twin-screw extruder.

38. 38. The method of claim 36 or 37, wherein the elevated temperature is from about 160°C to about 230°C.

39. 39. The method of any one of claims 36 to 38, wherein the twin screw extruder has a speed of about 60 rpm.

40. During either step (a) or step (b), Sb ２ O ３ 40. The method of any one of claims 36 to 39, further comprising adding:

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