A thermoplastic resin composition, its preparation method, and the resulting product.

Abstract

This application discloses a thermoplastic resin composition, its preparation method, and the resulting product, belonging to the field of polymer materials technology. This application simultaneously adds specific amounts of brominated polystyrene, dialkyl-substituted phosphinates, and monoalkyl-substituted phosphinates of specific weight-average molecular weights to a matrix resin including at least one of ABS, SAN, and HIPS. By utilizing their synergistic effect, the resulting thermoplastic resin composition exhibits good flame retardancy, strong resistance to heat distortion, and is less prone to tiger-skin patterns during injection molding, making it suitable for manufacturing electronic and electrical products.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, specifically to a thermoplastic resin composition and its preparation method and components. Background Technology

[0002] Thermoplastic resins such as ABS (acrylonitrile-butadiene-styrene copolymer), SAN (acrylonitrile-styrene copolymer), and HIPS (high-impact polystyrene) are widely used in electronics and electrical fields due to their excellent mechanical properties. However, these materials themselves have problems such as poor flame retardancy and easy deformation when heated, which greatly limits the further expansion of their application scenarios.

[0003] CN105419143A discloses a heat-resistant ASA resin composition for eliminating tiger-stripe patterns. It introduces a low molecular weight styrene-acrylonitrile copolymer as a tiger-stripe improver into a matrix resin formed from ASA rubber powder and SAN resin, effectively improving the appearance defect. However, this composition degrades the heat distortion temperature. CN117820795A, on the other hand, combines a specific amount of star-shaped SBS block copolymer and a specific mineral oil into a HIPS matrix, significantly improving the material's drop resistance and reducing injection molding tiger-stripe defects. However, this system also suffers from heat distortion temperature degradation.

[0004] Therefore, how to make this type of material have both good flame retardancy and heat deformation resistance, and how to prevent tiger-skin patterns from forming during injection molding, has become an urgent technical problem to be solved. Summary of the Invention

[0005] Based on the deficiencies of the existing technology, the purpose of this application is to provide a thermoplastic resin composition, its preparation method and the finished product thereof. The thermoplastic resin composition not only has good flame retardancy, but also strong resistance to heat deformation, and is not prone to tiger-skin pattern formation during injection molding.

[0006] To achieve the above objectives, in a first aspect, this application provides a thermoplastic resin composition comprising the following components in parts by weight: 100 parts of matrix resin, 12-24 parts of brominated polystyrene, 5.8-9.5 parts of dialkyl-substituted hypophosphite, and 0.2-1.4 parts of monoalkyl-substituted hypophosphite. The matrix resin includes at least one of ABS, SAN resin, and HIPS. The weight-average molecular weight of the brominated polystyrene is 5,000 to 140,000. The dialkyl-substituted phosphonate is at least one of the compounds of formula I, and the monoalkyl-substituted phosphonate is at least one of the compounds of formula II. , Among them, R 1 R2 and R 3 Each group is independently selected from the following groups: C1~C8 straight-chain alkyl, C3~C8 branched alkyl, C3~C8 cycloalkyl, C7~C8 aralkyl, and aromatic groups; X and Y are each independently selected from Al, Mg, Ca, Zn, Ti, or Fe; n and m are each independently selected from integers between 2 and 4.

[0007] By simultaneously adding specific amounts of brominated polystyrene, dialkyl-substituted phosphinate, and monoalkyl-substituted phosphinate with specific weight-average molecular weight to the matrix resin, the thermoplastic resin composition exhibits good flame retardancy, strong resistance to heat deformation, and is less prone to tiger-skin pattern formation during injection molding due to the synergistic effect of the above components.

[0008] In Equations I and II, R 1 R 2 and R 3 They can be completely different, or two or three of them can be the same; X and Y can be the same or different; n and m can be the same or different.

[0009] For example, the C1 to C8 straight-chain alkyl group is at least one of C1, C2, C3, C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0010] For example, the C3-C8 branched alkyl group is at least one of C3, C4, C5, C6, C7, or C8 branched alkyl groups. In some embodiments, the C3-C8 branched alkyl group is at least one of (CH3)2CH-, (CH3)2CHCH2-, (CH3)3C-, (CH3)2CHCH2CH2-, CH3CH2CH(CH3)CH2-, (CH3)3CCH2-, (CH3)2CHCH2CH2CH2-, CH3CH(CH3)CH2CH2CH2-, (CH3)2CHCH2CH2CH2CH2-, CH3CH2CH2CH2CH(CH3)CH2-, (CH3CH2)2CHCH2CH2-, (CH3)2CHCH2C(CH3)2CH2-, CH3CH2CH(CH2CH3)CH2CH2CH2-, or CH3CH2CH2CH2CH2CH(CH3)CH2-.

[0011] For example, the C3 to C8 cycloalkyl group is at least one of C3, C4, C5, C6, C7 or C8 cycloalkyl groups.

[0012] For example, the C7-C8 aralkyl group is at least one of C7 and C8 aralkyl groups. In the C7-C8 aralkyl group, the alkyl portion can be straight-chain or branched; the aromatic portion can be phenyl.

[0013] For example, aromatic groups include, but are not limited to, phenyl groups.

[0014] For example, n is selected from 2, 3 or 4.

[0015] For example, m is selected from 2, 3 or 4.

[0016] Preferably, R 1 and R 2 Each group is independently selected from the following groups: C1~C8 straight-chain alkyl, C3~C8 branched alkyl or C7~C8 aralkyl, which not only have excellent stability but are also easy to synthesize.

[0017] Preferably, the matrix resin has a weight percentage of 65% or more in the thermoplastic resin composition, such as any two of the following ranges: 65%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 84.2%, or more.

[0018] For example, the brominated polystyrene is within a range of any two of 12 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, or more.

[0019] For example, the dialkyl-substituted phosphonate is in the range of 5.8 parts by weight, 6 parts by weight, 6.2 parts by weight, 6.4 parts by weight, 6.6 parts by weight, 6.8 parts by weight, 7 parts by weight, 7.2 parts by weight, 7.4 parts by weight, 7.6 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.4 parts by weight, 8.6 parts by weight, 8.8 parts by weight, 9 parts by weight, 9.2 parts by weight, 9.5 parts by weight, or any two of the above.

[0020] For example, the monoalkyl-substituted phosphonate is in the range of any two of the following: 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, or more.

[0021] For example, the weight-average molecular weight of the brominated polystyrene is within the range formed by any two of the following: 5,000, 8,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, or higher. The weight-average molecular weight of the brominated polystyrene is obtained by gel permeation chromatography (GPC).

[0022] Preferably, the weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is (4.5~39.5):1, such as 4.7:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 39:1, or any range formed by two or more of these. More preferably, the weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is (8.5~19.5):1.

[0023] When the weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is in the range of (4.5~39.5):1, especially in the range of (8.5~19.5):1, it is more conducive to improving the flame retardancy of the thermoplastic resin composition.

[0024] Preferably, the weight ratio of the brominated polystyrene to the total weight of the dialkyl-substituted phosphinate and the monoalkyl-substituted phosphinate is (1.3~3.2):1, such as 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, or any two of the above ranges. More preferably, the weight ratio of the brominated polystyrene to the total weight of the dialkyl-substituted phosphinate and the monoalkyl-substituted phosphinate is (1.7~2.6):1.

[0025] When the weight ratio of the brominated polystyrene to the total weight of the dialkyl-substituted phosphonate and the monoalkyl-substituted phosphonate is in the range of (1.3~3.2):1, especially in the range of (1.7~2.6):1, it is more conducive to the balance of flame retardancy, heat distortion resistance and ability to suppress tiger stripe formation of the thermoplastic resin composition.

[0026] Preferably, the dialkyl-substituted phosphinate includes aluminum diethylphosphinate, aluminum di-n-propylphosphinate, aluminum diisopropylphosphinate, aluminum di-n-butylphosphinate, aluminum diisobutylphosphinate, aluminum di-n-pentylphosphinate, aluminum diisopentylphosphinate, aluminum di-n-hexylphosphinate, aluminum di-n-heptylphosphinate, aluminum di-n-octylphosphinate, aluminum diphenylethylphosphinate, zinc diethylphosphinate, zinc di-n-propylphosphinate, zinc diisopropylphosphinate, zinc diisopropylphosphinate, zinc diisobutylphosphinate, and aluminum diisopropylphosphinate. Zinc butylphosphinate, zinc di-n-pentylphosphinate, zinc di-isopentylphosphinate, zinc di-n-hexylphosphinate, zinc di-n-heptylphosphinate, zinc di-n-octylphosphinate, zinc diphenylethylphosphinate, magnesium diethylphosphinate, magnesium di-n-propylphosphinate, magnesium di-isopropylphosphinate, magnesium di-n-butylphosphinate, magnesium di-isobutylphosphinate, magnesium di-n-pentylphosphinate, magnesium di-isopentylphosphinate, magnesium di-n-hexylphosphinate, magnesium di-n-heptylphosphinate, magnesium di-n-octylphosphinate, zinc diphenylethylphosphinate Magnesium diphosphinate, titanium diethylphosphinate, titanium di-n-propylphosphinate, titanium diisopropylphosphinate, titanium di-n-butylphosphinate, titanium diisobutylphosphinate, titanium di-n-pentylphosphinate, titanium diisopentylphosphinate, titanium di-n-hexylphosphinate, titanium di-n-heptylphosphinate, titanium di-n-octylphosphinate, titanium diphenylethylphosphinate, calcium diethylphosphinate, calcium di-n-propylphosphinate, calcium diisopropylphosphinate, calcium di-n-butylphosphinate, calcium diisobutylphosphinate, calcium di-n-pentylphosphinate At least one of the following: calcium phosphonate, diisopentyl calcium phosphonate, di-n-hexyl calcium phosphonate, di-n-heptyl calcium phosphonate, di-n-octyl calcium phosphonate, diphenylethyl calcium phosphonate, diethylferric phosphonate, di-n-propylferric phosphonate, diisopropylferric phosphonate, di-n-butylferric phosphonate, diisobutylferric phosphonate, di-n-pentylferric phosphonate, diisopentylferric phosphonate, di-n-heptylferric phosphonate, di-n-octylferric phosphonate, and diphenylethylferric phosphonate.

[0027] Preferably, the monoalkyl-substituted phosphinate includes aluminum ethylphosphinate, aluminum n-propylphosphinate, aluminum isopropylphosphinate, aluminum n-butylphosphinate, aluminum isobutylphosphinate, aluminum n-pentylphosphinate, aluminum isopentylphosphinate, aluminum n-hexylphosphinate, aluminum n-heptylphosphinate, aluminum n-octylphosphinate, aluminum cyclohexylphosphinate, aluminum phenylphosphinate, aluminum benzylphosphinate, aluminum phenylethylphosphinate, zinc ethylphosphinate, zinc n-propylphosphinate, zinc isopropylphosphinate, zinc n-butylphosphinate, zinc isobutylphosphinate, and zinc n-pentylphosphinate. Zinc phosphonate, zinc isopentyl phosphonate, zinc n-hexyl phosphonate, zinc n-heptyl phosphonate, zinc n-octyl phosphonate, zinc cyclohexyl phosphonate, zinc phenyl phosphonate, zinc benzyl phosphonate, zinc phenethyl phosphonate, magnesium ethyl phosphonate, magnesium n-propyl phosphonate, magnesium isopropyl phosphonate, magnesium n-butyl phosphonate, magnesium isobutyl phosphonate, magnesium n-pentyl phosphonate, magnesium isopentyl phosphonate, magnesium n-hexyl phosphonate, magnesium n-heptyl phosphonate, magnesium n-octyl phosphonate, magnesium cyclohexyl phosphonate, magnesium phenyl phosphonate, magnesium benzyl phosphonate, magnesium phenyl phosphonate, magnesium phenethyl phosphonate, magnesium phenyl ... Magnesium phosphinate, Titanium ethyl phosphinate, Titanium n-propyl phosphinate, Titanium isopropyl phosphinate, Titanium n-butyl phosphinate, Titanium isobutyl phosphinate, Titanium n-pentyl phosphinate, Titanium isopentyl phosphinate, Titanium n-hexyl phosphinate, Titanium n-heptyl phosphinate, Titanium n-octyl phosphinate, Titanium cyclohexyl phosphinate, Titanium phenyl phosphinate, Titanium benzyl phosphinate, Titanium phenylethyl phosphinate, Calcium ethyl phosphinate, Calcium n-propyl phosphinate, Calcium isopropyl phosphinate, Calcium n-butyl phosphinate, Calcium isobutyl phosphinate, Calcium n-pentyl phosphinate, Calcium isopentyl phosphinate At least one of the following: calcium hexylphosphonate, calcium heptylphosphonate, calcium octylphosphonate, calcium cyclohexylphosphonate, calcium phenylphosphonate, calcium benzylphosphonate, calcium phenylethylphosphonate, iron ethylphosphonate, iron propylphosphonate, iron isopropylphosphonate, iron butylphosphonate, iron isobutylphosphonate, iron pentylphosphonate, iron isopentylphosphonate, iron hexylphosphonate, iron heptylphosphonate, iron octylphosphonate, iron cyclohexylphosphonate, iron phenylphosphonate, iron benzylphosphonate, and iron phenylethylphosphonate.

[0028] In some embodiments, the di(or mono)alkyl-substituted phosphonates can be commercially available or prepared using conventional methods in the art, including but not limited to the methods described below. For example, a method for preparing di(or mono)alkyl-substituted phosphonates includes the following steps: Sodium di(or mono)alkyl-substituted hypophosphonates are mixed with water-soluble salts to undergo a metathesis reaction, yielding di(or mono)alkyl-substituted hypophosphonate products.

[0029] Among them, dialkyl-substituted sodium hypophosphite is at least one of the compounds of formula III. ； Among them, R 1 and R 2Each group is independently selected from the following groups: C1~C8 straight-chain alkyl, C3~C8 branched alkyl, C3~C8 cycloalkyl, C7~C8 aralkyl, and aromatic group.

[0030] In Formula III, R 1 and R 2 They can be the same, yet they can also be different.

[0031] In Equation III, when R 1 and / or R 2 When selected from C1-C8 straight-chain alkyl groups, the C1-C8 straight-chain alkyl groups can be at least one of C1, C2, C3, C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0032] In Equation III, when R 1 and / or R 2 When selected from C3-C8 branched alkyl groups, the C3-C8 branched alkyl groups can be at least one of C3, C4, C5, C6, C7 or C8 branched alkyl groups. In one embodiment, the C3-C8 branched alkyl group is at least one of (CH3)2CH-, (CH3)2CHCH2-, (CH3)3C-, (CH3)2CHCH2CH2-, CH3CH2CH(CH3)CH2-, (CH3)3CCH2-, (CH3)2CHCH2CH2CH2-, CH3CH(CH3)CH2CH2CH2-, (CH3)2CHCH2CH2CH2CH2-, CH3CH2CH2CH2CH(CH3)CH2-, (CH3CH2)2CHCH2CH2-, (CH3)2CHCH2C(CH3)2CH2-, CH3CH2CH(CH2CH3)CH2CH2CH2-, or CH3CH2CH2CH2CH2CH(CH3)CH2-.

[0033] In Equation III, when R 1 and / or R 2 When selected from C3-C8 cycloalkyl groups, the C3-C8 cycloalkyl group can be at least one of C3, C4, C5, C6, C7, or C8 cycloalkyl groups.

[0034] In Equation III, when R 1 and / or R 2 When selected from C7-C8 aralkyl groups, the C7-C8 aralkyl group can be at least one of C7 and C8 aralkyl groups. In a C7-C8 aralkyl group, the alkyl moiety can be straight-chain or branched; the aromatic moiety can be phenyl.

[0035] In Equation III, when R 1 and / or R 2 When selected from aromatic groups, the aromatic group can be phenyl.

[0036] In some embodiments, the dialkyl-substituted sodium hypophosphite used includes at least one of sodium diethylphosphite, sodium di-n-propylphosphite, sodium diisopropylphosphite, sodium di-n-butylphosphite, sodium diisobutylphosphite, sodium di-n-pentylphosphite, sodium di-n-hexylphosphite, sodium di-n-heptylphosphite, and sodium di-n-octylphosphite.

[0037] Sodium hypophosphite with a monoalkyl substituted group is at least one of the compounds of formula IV. ; R 3 Selected from the following groups: C1~C8 straight-chain alkyl, C3~C8 branched alkyl, C3~C8 cycloalkyl, C7~C8 aralkyl, aromatic group.

[0038] In Equation IV, when R 3 When selected from C1 to C8 straight-chain alkyl groups, the C1 to C8 straight-chain alkyl groups can be C1, C2, C3, C4, C5, C6, C7, or C8 straight-chain alkyl groups.

[0039] In Equation IV, when R 3 When selected from C3-C8 branched alkyl groups, the C3-C8 branched alkyl groups can be C3, C4, C5, C6, C7 or C8 branched alkyl groups. In one embodiment, the C3-C8 branched alkyl group is (CH3)2CH-, (CH3)2CHCH2-, (CH3)3C-, (CH3)2CHCH2CH2-, CH3CH2CH(CH3)CH2-, (CH3)3CCH2-, (CH3)2CHCH2CH2CH2-, CH3CH(CH3)CH2CH2CH2-, (CH3)2CHCH2CH2CH2CH2-, CH3CH2CH2CH2CH(CH3)CH2-, (CH3CH2)2CHCH2CH2-, (CH3)2CHCH2C(CH3)2CH2-, CH3CH2CH(CH2CH3)CH2CH2CH2-, or CH3CH2CH2CH2CH2CH(CH3)CH2-.

[0040] In Equation IV, when R 3 When selected from C3 to C8 cycloalkyl groups, the C3 to C8 cycloalkyl groups can be C3, C4, C5, C6, C7, or C8 cycloalkyl groups.

[0041] In Equation IV, when R 3 When selected from C7-C8 aralkyl groups, the C7-C8 aralkyl group can be at least one of C7 and C8 aralkyl groups. In a C7-C8 aralkyl group, the alkyl moiety can be straight-chain or branched; the aromatic moiety can be phenyl.

[0042] In Equation IV, when R 3 When selected from aromatic groups, the aromatic group can be phenyl.

[0043] In some embodiments, the monoalkyl-substituted sodium hypophosphite used includes at least one of sodium ethyl phosphite, sodium n-propyl phosphite, sodium isopropyl phosphite, sodium n-butyl phosphite, sodium isobutyl phosphite, and sodium phenyl phosphite.

[0044] The water-soluble salt is a water-soluble salt of at least one metal selected from Al, Mg, Ca, Zn, Ti, and Fe. In some embodiments, the water-soluble salt is at least one selected from water-soluble chloride, water-soluble nitrate, and water-soluble sulfate. For example, the water-soluble salt includes at least one selected from aluminum nitrate, aluminum sulfate, magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, zinc chloride, zinc nitrate, zinc sulfate, ferric chloride, ferric nitrate, and ferric sulfate.

[0045] In one embodiment, when sodium di(or mono)alkyl-substituted phosphonate undergoes a metathesis reaction with a water-soluble salt, the reaction temperature is controlled at 80-90°C.

[0046] In one embodiment, the molar ratio of di(or mono)alkyl-substituted sodium hypophosphite to the water-soluble salt is (0.5~8):1.

[0047] In one embodiment, before mixing the obtained di(or mono)alkyl-substituted sodium hypophosphite with the water-soluble salt, the di(or mono)alkyl-substituted sodium hypophosphite is diluted with a solvent to a content of 20wt% to 40wt%, and the pH value is adjusted to between 2 and 3 with an acid. The solvent can be water, etc.; the acid used to adjust the pH value can be sulfuric acid, etc.

[0048] In one embodiment, when di(or mono)alkyl-substituted sodium hypophosphite is mixed with a water-soluble salt, the water-soluble salt is introduced in the form of a solution, wherein the content of the water-soluble salt in the solution is 20wt% to 25wt%.

[0049] In one embodiment, the metathesis reaction is carried out under an inert atmosphere. The inert atmosphere may be nitrogen or / or argon.

[0050] In one embodiment, the preparation method of the di(or mono)hydrocarbon substituted phosphonate further includes the following steps: after metathesis reaction, crystallization, solid-liquid separation, washing, and drying.

[0051] Di(or mono) alkyl-substituted phosphonates can also be prepared by other methods, such as the free radical addition method described in the literature (Zhang Mengting. Synthesis Research of Novel Phosphorus Flame Retardants [D]. Southeast University, 2022).

[0052] In some embodiments, the thermoplastic resin composition further includes the following component in parts by weight: 0.1 to 1 part of an anti-drip agent. Exemplarily, the anti-drip agent is in the range of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 part by weight, or any combination thereof. Adding an anti-drip agent improves anti-drip properties and flame retardancy, which is beneficial for achieving a thin-walled UL94 V-0 rating.

[0053] In some embodiments, the anti-dripping agent includes at least one of polytetrafluoroethylene (PTFE), styrene-acrylonitrile random copolymer coated PTFE, styrene-methyl methacrylate copolymer coated PTFE, and silicone resin coated PTFE.

[0054] In some embodiments, the melt index of the ABS at a temperature of 220°C and a load of 10kg is 8~83g / 10min, and the ABS contains 11%~36% acrylonitrile, 9%~36% butadiene, and 29%~78% styrene by weight.

[0055] In some embodiments, the ABS has a core-shell structure and / or an island-like structure. ABS can be produced by bulk polymerization or by emulsion polymerization, such as by blending butadiene-grafted SAN copolymers obtained by emulsion polymerization with SAN, and can also be commercially available.

[0056] In some embodiments, the SAN resin has a melt index of 5 to 100 g / 10 min at a temperature of 220°C and a load of 10 kg, and the SAN resin contains 17% to 36% acrylonitrile by weight.

[0057] In some embodiments, the matrix resin includes ABS high-resin powder and SAN resin, with the weight ratio of ABS high-resin powder to SAN being 2:8 to 4:6. The butadiene content in the ABS high-resin powder can be selected as 55% to 70%; the melt index of the SAN resin at 220°C and a load of 10 kg can be selected as 5 to 100 g / 10 min; and the weight percentage of acrylonitrile in the SAN resin can be selected as 17% to 36%.

[0058] In some embodiments, the HIPS has a melt index of 3~16 g / 10 min at a temperature of 200°C and a load of 5 kg, and the butadiene content in the HIPS is 7%~19%.

[0059] The weight percentage of monomer units in ABS and ABS high-resin powder was determined by elemental analysis combined with infrared spectroscopy.

[0060] The weight percentage of a single cell in a SAN is determined by elemental analysis.

[0061] The weight percentage of a single unit cell in HIPS was determined by infrared spectroscopy.

[0062] The melt flow index of ABS, SAN and HIPS was measured according to GB / T 3682-2000.

[0063] In some embodiments, the bromine content in the thermoplastic resin composition is 6% to 13% by mass, such as within the range of any two of 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or more.

[0064] In some embodiments, the brominated polystyrene contains 66% to 68% bromine by mass, such as 66%, 67%, or 68%.

[0065] The mass percentage of bromine in the brominated polystyrene was determined by high-temperature alkali fusion-potential titration, as follows: Accurately weigh 0.30 g of brominated polystyrene sample powder, add 1.0 g of solid Na₂CO₃ and 3.5 g of solid NaOH, heat until the alkali is molten, and continue heating until the brominated polystyrene sample powder is fully absorbed by the alkali (i.e., the brominated polystyrene sample powder completely disappears). Cool, add water to dissolve the sample, transfer to a 250 mL volumetric flask, dilute to volume, shake well, accurately pipette 5 mL of the sample solution into a titration cup, add 50 mL of water and 10 mL of nitric acid solution (68 wt%), stir to disperse, and titrate to the endpoint with silver nitrate standard titration solution. Calculate the mass percentage of bromine content based on the titration results.

[0066] In some embodiments, the thermoplastic resin composition further includes 0-3 parts by weight of processing aids, such as 0, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, or any range formed by two or more of these.

[0067] Preferably, the thermoplastic resin composition includes 0.5-3 parts by weight of processing aids.

[0068] Preferably, the processing aid includes an antioxidant.

[0069] The antioxidant can be selected with reference to existing technologies, such as at least one of hindered phenolic antioxidants, phosphite antioxidants, divalent sulfur antioxidants, hindered amine antioxidants, benzofuranone antioxidants, etc.

[0070] Specifically, the hindered phenolic antioxidants include, but are not limited to, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 1330), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid (antioxidant 3114), 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (antioxidant 1024), and triethylene glycol. Ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (antioxidant 1790), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA), 2-tert-butyl-6-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-4-methylphenyl acrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate (antioxidant GM), 2,6-di-tert-butyl-4-methylphenol (antioxidant 264), styrene-modified phenol (anti-aging agent SP), 2, At least one of 2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246); The phosphite antioxidants include, but are not limited to, at least one of the following: tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (antioxidant 9228), tris(nonylphenyl)phosphite (antioxidant TNP), bis(4-octylphenol) diphosphate (antioxidant 1093); The divalent sulfur antioxidants include, but are not limited to, at least one of dilaurate thiodipropionate (DLTP), distearate thiodipropionate (DSTP), and pentaerythritol tetra(3-lauryl thiopropionate) (antioxidant 412S); The hindered amine antioxidants include, but are not limited to, at least one of the following: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (LS-744), sebacate bis-2,2,6,6-tetramethylpiperidinol ester (LS-770), tris(1,2,2,6,6-pentamethylpiperidinol) phosphite (GW-540), and 4,4'-adipamide diaminobis(2,2,6,6-tetramethylpiperidin-1-oxy) (FlamstabNOR116); The benzofuranone antioxidants include, but are not limited to, at least one of 5,7-bis(1,1-dimethylethyl)-3-[2,3-dimethylphenyl]-2(3H)-benzofuranone (antioxidant 136) and 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl 3,5-di-tert-butyl-4-hydroxybenzoate (antioxidant 501).

[0071] Other additives may be added to the thermoplastic resin composition as needed to improve properties such as thermal stability, processability, weather resistance, and / or color. In some embodiments, the other additives include at least one of lubricants, weather-resistant agents, colorants, and antistatic agents.

[0072] The lubricant can be selected with reference to existing technologies, such as at least one of amide lubricants, stearate lubricants, ester lubricants, silicone lubricants, etc.

[0073] Specifically, the amide lubricants include, but are not limited to, at least one of erucamide, methyl bis-stearamide, or N,N-ethylene bis-stearamide; The stearate lubricants include, but are not limited to, at least one of calcium stearate, magnesium stearate, zinc stearate, or barium stearate; The ester lubricants include, but are not limited to, at least one of ethylene glycol stearate, glyceryl stearate, or pentaerythritol stearate; The silicone lubricant includes, but is not limited to, at least one of PE-based silicone masterbatch (e.g., silicone content 40 wt%~80 wt%), PP-based silicone masterbatch (e.g., silicone content 40 wt%~80 wt%), and SAN-based silicone masterbatch (e.g., silicone content 40 wt%~80 wt%).

[0074] The weathering agent can be selected with reference to existing technologies, such as at least one of benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers.

[0075] The colorant can be selected with reference to existing technologies, and includes, but is not limited to, at least one of pigments and dyes. Examples of pigments include titanium dioxide, phthalocyanine, ultramarine, iron oxide, or carbon black, and one or more of all organic pigments. Examples of dyes include one or more of azo yellow, quinacridone, perylene red, dioxazine, indolinone, isoindolin, anthraquinone blue, and anthraquinone violet.

[0076] The antistatic agent can be selected with reference to existing technologies, such as at least one of alkyl sulfonates, quaternary ammonium salts, glyceryl monostearate (GMS), ethoxylated alkylamines, polyether block amides (PEBA), carbon nanotubes, graphene, etc.

[0077] In some embodiments, the other adjuvants are 0 to 5.5 parts by weight, such as 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, or any range formed by two or more of the above.

[0078] According to a second aspect of this application, a method for preparing the thermoplastic resin composition is provided, comprising the following steps: mixing and dispersing the component raw materials, melt extruding, granulating, and obtaining the thermoplastic resin composition.

[0079] In some embodiments, melt extrusion and granulation are carried out in a twin-screw extruder when preparing the thermoplastic resin composition.

[0080] In some embodiments, the preparation method of the thermoplastic resin composition includes the following steps: weighing the material according to the formula amount, putting it into a mixer and mixing it at a speed of 800~1200 r / min for 3~8 min, then taking it out, putting the mixed material into the feed hopper of a twin-screw extruder, setting the process conditions, including the temperature setting range of each section of the extruder being 50~240℃, the screw speed being 200~800 r / min, the screw length-to-diameter ratio being 36:1~48:1, the feeding speed being 30~800 kg / h, and after melt blending in the twin-screw extruder, water cooling, drawing into strands, and pelletizing.

[0081] Thirdly, this application provides a component molded from the aforementioned thermoplastic resin composition. The molding method can be injection molding. For example, the component can be a part of electronic or electrical products such as a battery casing, a power tool casing, or an electronic control component casing.

[0082] Compared with the prior art, the beneficial effects of this application are as follows: This application simultaneously adds specific amounts of brominated polystyrene, dialkyl-substituted phosphinate and monoalkyl-substituted phosphinate of specific weight-average molecular weight to a matrix resin including at least one of ABS, SAN and HIPS. By utilizing their synergistic effect, it can ensure that the resulting thermoplastic resin composition has good flame retardancy, strong heat deformation resistance, and is not prone to tiger-skin pattern during injection molding, making it suitable for the preparation of electronic and electrical products. Detailed Implementation

[0083] To better illustrate the purpose, technical solutions, and advantages of this application, the following description, in conjunction with specific embodiments and comparative examples, aims to provide a detailed understanding of the content of this application, rather than limiting it. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this application are commonly used reagents and instruments. In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0084] The raw materials used in the following embodiments and comparative examples are shown below. Unless otherwise specified, all raw materials are commercially available. In addition, the same raw materials were used in each parallel experiment: ABS Resin 1: Bulk method, DOW, ABS 8434.

[0085] ABS Resin 2: Emulsion method, Ningbo LG Yongxing Chemical Co., Ltd., HI-121H.

[0086] ABS / SAN: ABS (KF-740 from Liaoning Kingfa Science & Technology Co., Ltd.) and SAN (310 NTR from Kumho Chemical Co., Ltd. of South Korea) were mixed and dispersed at a weight ratio of 3:7.

[0087] HIPS resin: Guoqiao Petrochemical Co., Ltd., PS 350K.

[0088] SAN resin: Liaoning Kingfa Science & Technology Co., Ltd., KFA-130.

[0089] Brominated polystyrene 1: Contains 66 wt% bromine, weight average molecular weight 2000, SR-1010, Shandong Xurui New Material Co., Ltd.

[0090] Brominated polystyrene 2: bromine content 68wt%, weight average molecular weight 5000, SR-3010, Shandong Xurui New Material Co., Ltd.

[0091] Brominated polystyrene 3: bromine content 67wt%, weight average molecular weight 50,000, SR-6010, Shandong Xurui New Material Co., Ltd.

[0092] Brominated polystyrene 4: bromine content 66wt%, weight average molecular weight 140,000, SAYTEX HP-3010, ALBEMARLE.

[0093] Brominated polystyrene 5: bromine content 68wt%, weight average molecular weight 200,000, SR-7010, Shandong Xurui New Material Co., Ltd.

[0094] Bromotriazine: 67wt% bromine content, FR-245, ICL-IP.

[0095] Dialkyl-substituted phosphonates 1: Aluminum diethylphosphonate, prepared as follows: Sodium diethylphosphonate is diluted with water to a concentration of 35 wt%, the pH is adjusted to 2.5 with sulfuric acid, and aluminum sulfate solution (aluminum sulfate content is 25 wt%) is added to carry out the reaction. The reaction is carried out under a nitrogen atmosphere and the reaction temperature is controlled at 85℃. After the reaction is completed, crystallize, filter, wash, and dry to obtain aluminum diethylphosphonate.

[0096] Dialkyl-substituted phosphinate 2: di-n-octylphosphinate aluminum, was prepared according to the process described in Sections 3.2.2 to 3.2.3 of the literature (Zhang Mengting. Synthesis Study of Novel Phosphorus Flame Retardants [D]. Southeast University, 2022).

[0097] Dialkyl-substituted phosphonate 3: aluminum diisopropylphosphonate, whose preparation method differs from that of dialkyl-substituted phosphonate 1 in that sodium diisopropylphosphonate is used instead of sodium diethylphosphonate.

[0098] Dihydro-substituted phosphonate 4: Zinc diethylphosphonate, the preparation method of which differs from that of dihydro-substituted phosphonate 1, is that zinc chloride solution (zinc chloride content of 22wt%) is used to completely replace aluminum sulfate solution.

[0099] Monoalkyl-substituted phosphonate 1: Aluminum ethylphosphonate, whose preparation method differs from that of dialkyl-substituted phosphonate 1 in that sodium ethylphosphonate is used instead of sodium diethylphosphonate.

[0100] Monoalkyl-substituted phosphonate 2: aluminum n-butylphosphonate, whose preparation method differs from that of monoalkyl-substituted phosphonate 1 in that sodium n-butylphosphonate is used instead of sodium ethylphosphonate.

[0101] Monoalkyl-substituted phosphinate 3: Aluminum phenylphosphinate, Hubei Chuyuebang New Material Technology Co., Ltd.

[0102] Monoalkyl-substituted phosphonate 4: Zinc ethylphosphonate, the preparation method of which differs from that of monoalkyl-substituted phosphonate 1, is that zinc chloride solution (zinc chloride content of 22wt%) is used to completely replace aluminum sulfate solution.

[0103] Hypophosphite: Al(H2PO2)3, Fujian Xin'an Technology Co., Ltd., FR605.

[0104] Melamine cyanurate (MCA): Jinan Jinyingtai Chemical Co., Ltd.

[0105] Anti-dripping agent 1: Styrene-methyl methacrylate copolymer coated polytetrafluoroethylene, DB109, Shanghai Puxin Polymer Materials Co., Ltd.

[0106] Anti-dripping agent 2: Polytetrafluoroethylene coated with styrene-acrylonitrile random copolymer, SN80-SA7, Guangzhou Entropy Energy Innovation Materials Co., Ltd.

[0107] Processing aid: A mixture of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], a phosphite antioxidant, and tris[2,4-di-tert-butylphenyl]phosphite, a hindered phenolic antioxidant, in a mass ratio of 1:2, commercially available.

[0108] The following examples and comparative examples all provide a thermoplastic resin composition, and their preparation methods include the following steps: Weigh the materials according to the formulas in Tables 1-3, put them into a mixer and mix at 1000 r / min for 5 minutes. Then take them out and put the mixed materials into the feed hopper of a twin-screw extruder. Set the process conditions, including the temperatures of each section of the extruder as 60℃, 120℃, 180℃, 200℃, 200℃, 200℃, 200℃, 200℃, 220℃, the screw speed as 500 r / min, the screw length-to-diameter ratio as 40:1, and the feeding speed as 35 kg / h. After melt blending in the twin-screw extruder, the materials are water-cooled, drawn into strands, and granulated to obtain a thermoplastic resin composition.

[0109] Table 1 Table 2 Table 3 The thermoplastic resin compositions of the above embodiments and comparative examples were subjected to the following performance tests: (1) Flame retardant performance: The thermoplastic resin composition was injection molded into a standard sample with a thickness of 2.0 mm. The vertical burning flame retardant performance of the sample was tested according to UL94-2023 standard, and the average value of t1+t2 was determined. (2) Heat distortion resistance: The thermoplastic resin composition was injection molded into standard specimens, and the heat distortion temperature of the specimens was tested according to ISO75-1-2020 standard under test conditions of 1.8MPa; (3) Tiger stripe pattern: The thermoplastic resin composition was molded in a rectangular injection mold. One set of samples was evaluated for comparison each time. The same injection molding machine and the same injection molding process parameters were used (using a high injection speed, which is 85% of the machine's maximum injection speed, as tiger stripe patterns are more likely to be generated under high-speed conditions). The mold temperature was fixed at 70℃. After the mold temperature stabilized, the tiger stripe pattern evaluation test was started, based on the maximum size of the tiger stripe pattern on the surface of the molded rectangular plate.

[0110] The test results are shown in Table 4.

[0111] Table 4 As can be seen from the above data, the thermoplastic resin compositions of each embodiment of this application have good flame retardancy, heat distortion resistance and the ability to suppress the formation of tiger stripes during injection molding, such as the average value of t1+t2 being less than 16s, the heat distortion temperature being above 80℃, and the maximum size of tiger stripes being less than 0.5cm.

[0112] Comparative Example 7 used other brominated flame retardants instead of brominated polystyrene, resulting in poor heat deformation resistance of the material. A comparison of Examples 1-3 and Comparative Examples 5-6 shows that controlling the weight-average molecular weight of brominated polystyrene between 0.5w and 14w is beneficial to balancing the flame retardancy, heat deformation resistance, and ability to suppress tiger-skin pattern formation of the thermoplastic resin composition.

[0113] Comparative Examples 1 and 2, lacking either hydrocarbon-substituted phosphinates or brominated polystyrene, exhibited deviations in the flame retardancy of their thermoplastic resin compositions, indicating that hydrocarbon-substituted phosphinates and brominated polystyrene synergistically improve flame retardancy.

[0114] Comparative Examples 3 and 4, lacking either dialkyl-substituted or monoalkyl-substituted phosphinates, exhibited significantly deteriorated flame retardancy in their thermoplastic resin compositions, indicating that dialkyl-substituted and monoalkyl-substituted phosphinates synergistically improve flame retardancy.

[0115] Comparative Examples 8 and 9 showed that the flame retardancy or heat distortion resistance of the thermoplastic resin compositions was significantly deteriorated due to the use of other flame retardants to replace the monohydrophosphinate.

[0116] As can be seen from the comparison of Examples 1, 4-7, when the weight ratio of dialkyl-substituted phosphonates to monoalkyl-substituted phosphonates is in the range of (8.5-19.5):1, it is more beneficial to improve the flame retardancy of the thermoplastic resin composition.

[0117] As can be seen from the comparison of Examples 1, 8-11, when the weight ratio of brominated polystyrene to the total weight of dialkyl-substituted phosphinate and monoalkyl-substituted phosphinate is in the range of (1.7-2.6):1, it is more conducive to the balance of flame retardancy, heat deformation resistance and ability to suppress tiger stripe formation of the thermoplastic resin composition.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A thermoplastic resin composition, characterized in that, It includes the following components in parts by weight: 100 parts of matrix resin, 12-24 parts of brominated polystyrene, 5.8-9.5 parts of dialkyl-substituted phosphonates, and 0.2-1.4 parts of monoalkyl-substituted phosphonates; The matrix resin includes at least one of ABS, SAN resin, and HIPS; The weight-average molecular weight of the brominated polystyrene is 5,000 to 140,000. The dialkyl-substituted phosphonate is at least one of the compounds of formula I, and the monoalkyl-substituted phosphonate is at least one of the compounds of formula II. ， Among them, R 1 R 2 and R 3 Each group is independently selected from the following groups: C1~C8 straight-chain alkyl, C3~C8 branched alkyl, C3~C8 cycloalkyl, C7~C8 aralkyl, and aromatic groups; X and Y are each independently selected from Al, Mg, Ca, Zn, Ti, or Fe; n and m are each independently selected from integers between 2 and 4.

2. The thermoplastic resin composition according to claim 1, characterized in that, The weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is (4.5~39.5):

1.

3. The thermoplastic resin composition according to claim 1, characterized in that, The weight ratio of the brominated polystyrene to the total weight of the dialkyl-substituted phosphonate and the monoalkyl-substituted phosphonate is (1.3~3.2):

1.

4. The thermoplastic resin composition according to claim 1, characterized in that, The dialkyl-substituted phosphines include aluminum diethylphosphines, aluminum di-n-propylphosphines, aluminum diisopropylphosphines, aluminum di-n-butylphosphines, aluminum diisobutylphosphines, aluminum di-n-pentylphosphines, aluminum diisopentylphosphines, aluminum di-n-hexylphosphines, aluminum di-n-heptylphosphines, aluminum di-n-octylphosphines, aluminum diphenylethylphosphines, zinc diethylphosphines, zinc di-n-propylphosphines, zinc diisopropylphosphines, zinc di-n-butylphosphines, and zinc diisobutylphosphines. Zinc phosphonate, di-n-pentyl zinc phosphonate, di-isopentyl zinc phosphonate, di-n-hexyl zinc phosphonate, di-n-heptyl zinc phosphonate, di-n-octyl zinc phosphonate, diphenylethyl zinc phosphonate, diethyl magnesium phosphonate, di-n-propyl magnesium phosphonate, di-isopropyl magnesium phosphonate, di-n-butyl magnesium phosphonate, di-isobutyl magnesium phosphonate, di-n-pentyl magnesium phosphonate, di-isopentyl magnesium phosphonate, di-n-hexyl magnesium phosphonate, di-n-heptyl magnesium phosphonate, di-n-octyl magnesium phosphonate, diphenylethyl zinc phosphonate Magnesium phosphonate, diethylphosphonate titanium, di-n-propylphosphonate titanium, diisopropylphosphonate titanium, di-n-butylphosphonate titanium, diisobutylphosphonate titanium, di-n-pentylphosphonate titanium, diisopentylphosphonate titanium, di-n-hexylphosphonate titanium, di-n-heptylphosphonate titanium, di-n-octylphosphonate titanium, diphenylethylphosphonate titanium, calcium diethylphosphonate, calcium di-n-propylphosphonate, calcium diisopropylphosphonate, calcium di-n-butylphosphonate, calcium diisobutylphosphonate, di-n-pentylphosphonate The first of the following: calcium phosphite, diisopentyl calcium phosphite, di-n-hexyl calcium phosphite, di-n-heptyl calcium phosphite, di-n-octyl calcium phosphite, diphenylethyl calcium phosphite, diethylferric phosphite, di-n-propylferric phosphite, diisopropylferric phosphite, di-n-butylferric phosphite, diisobutylferric phosphite, di-n-pentylferric phosphite, diisopentylferric phosphite, di-n-hexylferric phosphite, di-n-heptylferric phosphite, and diphenylethylferric phosphite.

5. The thermoplastic resin composition according to claim 1, characterized in that, The monoalkyl-substituted phosphinates include aluminum ethylphosphinate, aluminum n-propylphosphinate, aluminum isopropylphosphinate, aluminum n-butylphosphinate, aluminum isobutylphosphinate, aluminum n-pentylphosphinate, aluminum isopentylphosphinate, aluminum n-hexylphosphinate, aluminum n-heptylphosphinate, aluminum n-octylphosphinate, aluminum cyclohexylphosphinate, aluminum phenylphosphinate, aluminum benzylphosphinate, aluminum phenethylphosphinate, zinc ethylphosphinate, zinc n-propylphosphinate, zinc isopropylphosphinate, zinc n-butylphosphinate, zinc isobutylphosphinate, and zinc n-pentylphosphinate. Zinc isopentyl phosphinate, zinc n-hexyl phosphinate, zinc n-heptyl phosphinate, zinc n-octyl phosphinate, zinc cyclohexyl phosphinate, zinc phenyl phosphinate, zinc benzyl phosphinate, zinc phenethyl phosphinate, magnesium ethyl phosphinate, magnesium n-propyl phosphinate, magnesium isopropyl phosphinate, magnesium n-butyl phosphinate, magnesium isobutyl phosphinate, magnesium n-pentyl phosphinate, magnesium isopentyl phosphinate, magnesium n-hexyl phosphinate, magnesium n-heptyl phosphinate, magnesium n-octyl phosphinate, magnesium cyclohexyl phosphinate, magnesium phenyl phosphinate, magnesium benzyl phosphinate, magnesium phenethyl phosphinate Magnesium phosphonate, ethyl phosphonate titanium, n-propyl phosphonate titanium, isopropyl phosphonate titanium, n-butyl phosphonate titanium, isobutyl phosphonate titanium, n-pentyl phosphonate titanium, isopentyl phosphonate titanium, n-hexyl phosphonate titanium, n-heptyl phosphonate titanium, n-octyl phosphonate titanium, cyclohexyl phosphonate titanium, phenyl phosphonate titanium, benzyl phosphonate titanium, phenylethyl phosphonate titanium, ethyl phosphonate calcium, n-propyl phosphonate calcium, isopropyl phosphonate calcium, n-butyl phosphonate calcium, isobutyl phosphonate calcium, n-pentyl phosphonate calcium, isopentyl phosphonate calcium At least one of the following: calcium hexylphosphonate, calcium heptylphosphonate, calcium octylphosphonate, calcium cyclohexylphosphonate, calcium phenylphosphonate, calcium benzylphosphonate, calcium phenylethylphosphonate, iron ethylphosphonate, iron propylphosphonate, iron isopropylphosphonate, iron butylphosphonate, iron isobutylphosphonate, iron pentylphosphonate, iron isopentylphosphonate, iron hexylphosphonate, iron heptylphosphonate, iron octylphosphonate, iron cyclohexylphosphonate, iron phenylphosphonate, iron benzylphosphonate, and iron phenylethylphosphonate.

6. The thermoplastic resin composition according to claim 1, characterized in that, The thermoplastic resin composition further includes the following components in parts by weight: 0.1 to 1 part of anti-dripping agent.

7. The thermoplastic resin composition according to claim 1, characterized in that, At least one of conditions (1) to (4) must be met: (1) The melt index of the ABS under the conditions of 220℃ and 10kg load is 8~83g / 10min, and the weight percentage of acrylonitrile in the ABS is 11%~36%, the weight percentage of butadiene is 9%~36%, and the weight percentage of styrene is 29%~78%; (2) The melt index of the SAN resin at a temperature of 220℃ and a load of 10kg is 5~100g / 10min, and the weight percentage of acrylonitrile in the SAN resin is 17%~36%; (3) The matrix resin includes ABS high-adhesion powder and SAN resin, and the weight ratio of ABS high-adhesion powder to SAN resin is 2:8~4:6; (4) The melt index of the HIPS at a temperature of 200℃ and a load of 5kg is 3~16g / 10min, and the butadiene content in the HIPS is 7%~19%; (5) The mass percentage of bromine in the thermoplastic resin composition is 6% to 13%.

8. The thermoplastic resin composition according to claim 1, characterized in that, It also includes 0.5-3 parts by weight of processing aids, including antioxidants.

9. The method for preparing the thermoplastic resin composition according to any one of claims 1 to 8, characterized in that, Includes the following steps: The raw materials are mixed and dispersed, melt-extruded, and granulated to obtain a thermoplastic resin composition.

10. A component, characterized in that, It is formed from the thermoplastic resin composition as described in any one of claims 1 to 8.

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