Abs composite and method of making and molded article

Abstract

This application discloses an ABS composite material, its preparation method, and molded parts, belonging to the field of polymer materials technology. This application achieves good flame retardancy by adding specific toughening agents, dialkyl-substituted phosphinates, monoalkyl-substituted phosphinates, and brominated flame retardants to ABS resin, and controlling the dosage of each component within a specific range. Simultaneously, the resulting composite material exhibits good flame retardancy, and the finished parts have a good appearance after painting, making it suitable for exterior parts of home appliances, two-wheeled electric vehicles, and other products.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, specifically to ABS composite materials and their preparation methods and molded parts. Background Technology

[0002] ABS resin is a terpolymer of acrylonitrile (A), butadiene (B), and styrene (S). It possesses excellent impact resistance, heat resistance, low-temperature resistance, dimensional stability, and surface gloss, making it widely used in the automotive, electronics, machinery, and construction industries. However, ABS itself has poor flame retardancy, making it difficult to meet the requirements of high flame retardancy applications. Furthermore, to improve aesthetics or weather resistance, ABS parts often require surface painting; however, painted surfaces are prone to surface defects such as spray marks, affecting product quality and market competitiveness.

[0003] CN102391608A combines an environmentally friendly brominated flame retardant with a flame retardant synergistic system composed of antimony trioxide, inorganic powder, and ultra-high molecular weight polysiloxane, enabling the vertical burning performance of ABS material to reach 3.2mm UL94 V-0 level, and even 1.6mm UL94 V-0. However, parts made from the resulting ABS composition are prone to appearance defects such as spray marks after painting.

[0004] CN105385058A discloses a low-stress, heat-resistant ABS resin, which uses ABS rubber powder, low-molecular-weight SAN resin, and high-acrylonitrile SAN resin as the matrix, and is compounded with heat-resistant agents, antioxidants, lubricants, and weather-resistant agents. It can be used for painted interior and exterior automotive parts, and can improve paint absorption after painting. However, this system still has significant shortcomings: on the one hand, its flame retardant properties are poor, and on the other hand, it is prone to spray marks after painting, making it difficult to meet high appearance requirements.

[0005] Therefore, there is an urgent need to develop an ABS composite material that combines excellent flame retardant properties with good appearance quality after painting. Summary of the Invention

[0006] Based on the deficiencies of the existing technology, the purpose of this application is to provide an ABS composite material, its preparation method and molded parts, wherein the ABS composite material has good flame retardancy and its parts have good appearance quality after painting.

[0007] To achieve the above objectives, in a first aspect, this application provides an ABS composite material comprising the following components in parts by weight: 50-78.5 parts of ABS resin, 3-15 parts of toughening agent, 3-13 parts of dialkyl-substituted phosphinate, 0.3-2.5 parts of monoalkyl-substituted phosphinate, and 13-20 parts of brominated flame retardant. The toughening agent includes at least one of methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene (CPE), polymethylsiloxane, and ASA (acrylonitrile-styrene-acrylate copolymer). 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 aryl 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.

[0008] The ABS composite material, under the synergistic effect of specific amounts of dihydro-substituted phosphinate, monohydro-substituted phosphinate, brominated flame retardant and specific toughening agent, has good flame retardancy. At the same time, its parts have a good appearance after painting, and it is suitable as an exterior material for products such as home appliance shells and two-wheeled electric vehicles.

[0009] The ABS resin is in the range of 50 to 78.5 parts by weight, such as 50 parts by weight, 52 parts by weight, 55 parts by weight, 57 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78.5 parts by weight, or any range formed by two or more of these. In some embodiments, the ABS resin is 61.5 to 76.5 parts by weight.

[0010] The toughening agent is 3 to 15 parts by weight, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, or any range formed by two or more of these. In some embodiments, the toughening agent is 4 to 10 parts by weight, which is more conducive to achieving a balance between flame retardancy and the appearance quality of the part after painting.

[0011] The dialkyl-substituted phosphonate is 3 to 13 parts by weight, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, or any two of the above ranges.

[0012] The monoalkyl-substituted phosphonate is 0.3 to 2.5 parts by weight, such as 0.3 parts by weight, 0.5 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, or any two of the above ranges.

[0013] The brominated flame retardant is 13 to 20 parts by weight, such as 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, or any two of the above ranges.

[0014] Preferably, the ABS resin accounts for more than 50% of the weight of the ABS composite material, such as the range formed by any two of the following: 50%, 52%, 55%, 57%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 78.5% or more.

[0015] Preferably, in the methyl methacrylate-butadiene-styrene copolymer, the weight percentage of methyl methacrylate is 11%~24%, the weight percentage of butadiene is 50%~80%, and the weight percentage of styrene is 9%~26%. Exemplarily, in the methyl methacrylate-butadiene-styrene copolymer, the weight percentage of methyl methacrylate is within the range of any two of 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or more. Exemplarily, in the methyl methacrylate-butadiene-styrene copolymer, the weight percentage of butadiene is within the range of any two of 50%, 55%, 60%, 65%, 70%, 75%, 80%, or more. For example, in the methyl methacrylate-butadiene-styrene copolymer, the weight percentage of styrene is within any two of the following ranges: 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%.

[0016] The weight percentage of each monomer in the methyl methacrylate-butadiene-styrene copolymer was determined by infrared spectroscopy.

[0017] Preferably, in the methyl methacrylate-butadiene-styrene copolymer, the rubber core is at least one of polybutadiene and butadiene-styrene copolymer SBR rubber, and the shell is at least one of a copolymer of methyl methacrylate and styrene and polymethyl methacrylate.

[0018] The methyl methacrylate-butadiene-styrene copolymer can be commercially available or prepared by conventional methods in the art, including but not limited to emulsion or suspension methods.

[0019] Preferably, the weight-average molecular weight of the chlorinated polyethylene is between 100,000 and 500,000. For example, the weight-average molecular weight of the chlorinated polyethylene is within the range formed by any two of the following: 100,000, 150,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, or higher. The weight-average molecular weight of the chlorinated polyethylene is obtained using gel permeation chromatography (GPC).

[0020] Preferably, the chlorinated polyethylene contains 20% to 45% chlorine by weight, such as within the range of 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 37%, 40%, 42%, 45%, or any two of the above. In some embodiments, the chlorinated polyethylene contains 25% to 35% chlorine by weight. The chlorine content in the chlorinated polyethylene is obtained by X-ray fluorescence analysis.

[0021] In some embodiments, the chlorinated polyethylene contains a separating agent, such as at least one of talc and calcium carbonate. In some embodiments, the weight percentage of the separating agent in the chlorinated polyethylene is 5% to 10%, such as within the range of any two of 5%, 6%, 7%, 8%, 9%, 10%, or more.

[0022] Preferably, the weight-average molecular weight of the polymethylsiloxane is 50,000 to 1,000,000, such as within the range formed by any two of the following: 50,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1,000,000 or higher. The weight-average molecular weight of the polymethylsiloxane is obtained by gel permeation chromatography (GPC).

[0023] Preferably, the polymethylsiloxane contains silicon at a weight percentage of 10% to 40%, such as within the range of any two of 10%, 15%, 20%, 25%, 30%, 35%, 40%, or higher. The weight percentage of silicon in the polymethylsiloxane is obtained by electro-coupled plasma atomic emission spectrometry.

[0024] Preferably, the ASA comprises monomer units in the following weight percentages: polymethylsiloxane 0-10%, butyl acrylate 50-60%, acrylonitrile 8-13%, and styrene 27-32%. For example, in the ASA, the weight percentage of polymethylsiloxane is within the range formed by any two of 0, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or more. For example, in the ASA, the weight percentage of butyl acrylate is within the range formed by any two of 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, or more. For example, in the ASA, the weight percentage of acrylonitrile is within the range formed by any two of 8%, 9%, 10%, 11%, 12%, 13%, or more. For example, in the ASA, the weight percentage of styrene is within the range formed by any two of 27%, 28%, 29%, 30%, 31%, 32%, or more.

[0025] The weight percentage of each monomer unit in ASA was determined by elemental analysis combined with infrared spectroscopy.

[0026] 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.

[0027] 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.

[0028] 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-.

[0029] For example, the C3 to C8 cycloalkyl group is at least one of C3, C4, C5, C6, C7 or C8 cycloalkyl groups.

[0030] 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.

[0031] For example, aromatic groups include, but are not limited to, phenyl groups.

[0032] For example, n is selected from 2, 3 or 4.

[0033] For example, m is selected from 2, 3 or 4.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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 following methods. 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 to obtain di(or mono)alkyl-substituted hypophosphonate products.

[0038] 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.

[0039] In Formula III, R 1 and R 2 They can be the same, yet they can also be different.

[0040] 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.

[0041] 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-.

[0042] 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.

[0043] 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.

[0044] In Equation III, when R 1 and / or R 2 When selected from aromatic groups, the aromatic group can be phenyl.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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-.

[0049] 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.

[0050] 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.

[0051] In Equation IV, when R 3 When selected from aromatic groups, the aromatic group can be phenyl.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] In one embodiment, the molar ratio of di(or mono)alkyl-substituted sodium hypophosphite to the water-soluble salt is (0.5~8):1.

[0056] In one embodiment, before mixing the 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.

[0057] 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%.

[0058] In one embodiment, the metathesis reaction is carried out under an inert atmosphere. The inert atmosphere may be nitrogen or / or argon.

[0059] 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.

[0060] 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).

[0061] Preferably, the bromine content in the bromine-based flame retardant is 50% to 83% by mass, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 83%.

[0062] The mass percentage of bromine in the brominated flame retardant was determined by high-temperature alkali fusion-potential titration, as follows: Accurately weigh 0.30 g of the brominated flame retardant sample powder, add 1.0 g of solid Na₂CO₃ and 3.5 g of solid NaOH, heat until the alkali becomes molten, and continue heating until the brominated flame retardant sample powder is fully absorbed by the alkali (i.e., the brominated flame retardant sample powder completely disappears). Cool, add water to dissolve the sample, pour into 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.

[0063] In some embodiments, the bromine content in the ABS composite material is 8.5% to 13% by mass, such as the range formed by any two of 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13% or more.

[0064] Preferably, the brominated flame retardant includes at least one selected from brominated triazine, brominated epoxy resin, decabromodiphenyl ethane, ethylene bis(tetrabromophthalimide), brominated polystyrene, polybrominated styrene, brominated polycarbonate, and pentabromobenzyl polyacrylate. More preferably, the brominated flame retardant includes at least one selected from brominated triazine, brominated polyimide, and brominated polystyrene to improve flame retardancy.

[0065] The brominated epoxy resin can be end-capped or unend-capped. In some embodiments, the end-capping groups are derived from phenolic compounds, such as tribromophenol.

[0066] In some embodiments, the weight-average molecular weight of the brominated epoxy resin is 700 to 3000, such as the range formed by any two of 700, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 3000 or above.

[0067] In some embodiments, the weight-average molecular weight of the brominated polystyrene is 3000 to 8000, such as the range formed by any two of the following: 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000 or above.

[0068] In some embodiments, the weight-average molecular weight of the polybrominated styrene is 3000 to 8000, such as the range formed by any two of the following: 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000 or above.

[0069] In some embodiments, the weight-average molecular weight of the brominated polycarbonate is 3500 to 8500, such as the range formed by any two of the following: 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500.

[0070] In some embodiments, the weight-average molecular weight of the polypentabromobenzyl acrylate is 500,000 to 700,000, such as the range formed by any two of the following: 500,000, 520,000, 540,000, 560,000, 580,000, 600,000, 620,000, 640,000, 660,000, 680,000, 700,000.

[0071] The weight-average molecular weights of the brominated epoxy resin, brominated polystyrene, polybrominated styrene, brominated polycarbonate, and pentabromobenzyl acrylate were obtained by gel permeation chromatography (GPC).

[0072] In some embodiments, the ABS composite material further includes an anti-drip agent, wherein the amount of the anti-drip agent is 0 to 0.5 parts by weight. In one embodiment, the amount of the anti-drip agent is 0.1 to 0.5 parts by weight to improve anti-drip performance, which is beneficial for achieving thin-walled UL-94 V-0.

[0073] 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.

[0074] In some embodiments, the ABS resin includes at least one of a mixture of ABS high-resin powder and SAN resin, and an acrylonitrile-butadiene-styrene terpolymer, wherein the mass ratio of the ABS high-resin powder to the SAN resin in the mixture is 1.5:8.5 to 3.7:6.3, such as 1.5:8.5, 2.4:7.6, 3.7:6.3 or any two of the above ranges.

[0075] In some embodiments, the butadiene weight percentage in the ABS high-resin powder is 55% to 65%, such as the range formed by any two of 55%, 58%, 60%, 62%, 64%, 65% or more.

[0076] In some embodiments, the melt index of the SAN resin at a temperature of 220°C and a load of 10 kg is 8 to 95 g / 10 min, such as 8 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 50 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min, 95 g / 10 min, or any two of the above ranges.

[0077] In some embodiments, the acrylonitrile content in the SAN resin is 20% to 35% by weight, such as a range formed by any two of 20%, 22%, 24%, 26%, 28%, 30%, 32%, 35%, or more.

[0078] In some embodiments, the melt index of the acrylonitrile-butadiene-styrene terpolymer at a temperature of 220°C and a load of 10 kg is 8 to 78 g / 10 min, such as 8 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 50 g / 10 min, 60 g / 10 min, 70 g / 10 min, 78 g / 10 min, or any two of the above ranges.

[0079] In some embodiments, the acrylonitrile-butadiene-styrene terpolymer contains 13% to 30% by weight of acrylonitrile, 6% to 30% by weight of butadiene, and 40% to 81% by weight of styrene. For example, the acrylonitrile-butadiene-styrene terpolymer contains acrylonitrile in the range of any two of the following: 13%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, or more. For example, the acrylonitrile-butadiene-styrene terpolymer contains butadiene in the range of any two of the following: 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, or more. For example, the acrylonitrile-butadiene-styrene terpolymer contains styrene in the range of any two of the following: 40%, 50%, 60%, 70%, 81%, or more.

[0080] In some embodiments, the ABS resin has a core-shell structure and / or an island-like structure. The ABS resin can be produced by bulk polymerization or by emulsion polymerization, such as by blending butadiene-grafted SAN copolymer obtained by emulsion polymerization with SAN resin; it can also be commercially available.

[0081] The weight percentage of monomer units in acrylonitrile-butadiene-styrene terpolymer and ABS high-rubber powder was determined by elemental analysis combined with infrared spectroscopy.

[0082] The weight percentage of monomer units in SAN resin was determined by elemental analysis.

[0083] The melt flow index of the acrylonitrile-butadiene-styrene terpolymer and SAN resin was measured according to GB / T 3682-2000.

[0084] Other additives may be added to the ABS composite material 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 antioxidants, lubricants, weather resistant agents, colorants, and antistatic agents.

[0085] 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.

[0086] 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).

[0087] In some embodiments, the antioxidant includes hindered phenolic antioxidants and phosphite antioxidants, wherein the weight ratio of the hindered phenolic antioxidants to the phosphite antioxidants is (1~3):1.

[0088] 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.

[0089] 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%).

[0090] 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.

[0091] 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.

[0092] 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.

[0093] In some embodiments, the other adjuvants are 0 to 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, or any range formed by two or more of the above.

[0094] Secondly, this application provides a method for preparing ABS composite material, comprising the following steps: mixing and dispersing the component raw materials, melt extrusion, granulation, and obtaining ABS composite material.

[0095] In one embodiment, melt extrusion and granulation are carried out in a twin-screw extruder when preparing the ABS composite material.

[0096] In one embodiment, the melt extrusion meets the following requirements: the melt extrusion temperature is 180~240℃, the screw speed is 200~800rpm, the screw length-to-diameter ratio is 36:1~48:1, and the feeding speed is 30~800kg / h.

[0097] Thirdly, this application provides a molded part, which is injection molded from the ABS composite material. The ABS composite material is suitable for manufacturing exterior parts for home appliances and two-wheeled electric vehicles, such as air conditioner outdoor unit housings, and outer shells and protective panels for two-wheeled electric vehicles.

[0098] In some implementations, the injection molding meets the following conditions: injection temperature 200~260°C.

[0099] In some embodiments, the surface of the molded part is provided with a paint layer.

[0100] Compared with the prior art, the beneficial effects of this application are as follows: By adding specific toughening agents, dihydro-substituted phosphinates, monohydro-substituted phosphinates and brominated flame retardants to ABS resin, and controlling the amount of each of the above components within a specific range, the resulting composite material has good flame retardancy. At the same time, its parts have a good appearance after painting, making it suitable for exterior parts of products such as home appliances and two-wheeled electric vehicles. Detailed Implementation

[0101] 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.

[0102] 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: 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.

[0103] 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).

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] Monoalkyl-substituted phosphinate 3: Aluminum phenylphosphinate, Hubei Chuyuebang New Material Technology Co., Ltd.

[0109] 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.

[0110] Melamine cyanurate (MCA): Jinan Jinyingtai Chemical Co., Ltd.

[0111] Bromine-based flame retardant 1: Brominated polystyrene, SR-3010, Shandong Xurui New Material Co., Ltd.

[0112] Brominated flame retardant 2: Bromotriazine, FR-245, ICL-IP.

[0113] Brominated flame retardant 3: Brominated epoxy resin, F-3014, ICL-IP.

[0114] Brominated flame retardant 4: Poly(pentabromobenzyl) acrylate, FR-1025, ICL-IP.

[0115] Brominated flame retardant 5: Ethylene bis(tetrabromophthalimide), BT-93, Albemarle, USA.

[0116] Anti-dripping agent 1: Styrene-acrylonitrile random copolymer coated with polytetrafluoroethylene, SN80-SA7, Guangzhou Entropy Energy Innovation Materials Co., Ltd.

[0117] Anti-dripping agent 2: Styrene-methyl methacrylate copolymer coated polytetrafluoroethylene, DB109, Shanghai Puxin Polymer Materials Co., Ltd.

[0118] ABS Resin 1: Emulsion method, HI-121H, Ningbo LG Yongxing Chemical Co., Ltd.

[0119] ABS Resin 2: Bulk method, ABS 8434, DOW.

[0120] ABS / SAN: ABS high-adhesion powder (INEOS Styrolution's MAG 50) and SAN resin (Kumho Chemical Co., Ltd.'s 310 NTR) were mixed and dispersed at a weight ratio of 3.5:6.5.

[0121] ABS high-adhesion powder: INEOSS Styrolution MAG 50.

[0122] 1. Methyl methacrylate-butadiene-styrene copolymer: The rubber core is polybutadiene, and the shell is a copolymer of methyl methacrylate and styrene. Model: EM500. LG Chem.

[0123] 2. Methyl methacrylate-butadiene-styrene copolymer: The rubber core is butadiene-styrene copolymer SBR rubber, and the shell is polymethyl methacrylate, model EXL-2620, Rohm and Haas International Trading (Shanghai) Co., Ltd.

[0124] Chlorinated polyethylene 1: CPE-132C, Hangzhou Keli Chemical Co., Ltd.

[0125] Chlorinated polyethylene 2: CPE2135, Weifang Yaxing Chemical Co., Ltd.

[0126] Polymethylsiloxane 1: AK60000, Wacker Chemie International GmbH, Germany.

[0127] Polymethylsiloxane 2: AK100000, Wacker Chemie International GmbH, Germany.

[0128] Additives: A mixture of hindered phenolic antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and phosphite antioxidant tris[2,4-di-tert-butylphenyl]phosphite, with a weight ratio of hindered phenolic antioxidant to phosphite antioxidant of 2:1, commercially available.

[0129] Examples 1-10 and Comparative Examples 1-7 These examples and comparative examples all provide an ABS composite material, and their preparation methods include the following steps: According to the formulations of ABS composite materials in Tables 1 and 2, the raw materials of each component are mixed and dispersed, fed into a twin-screw extruder for melt extrusion and granulation to obtain ABS composite materials. The twin-screw temperatures in the twin-screw extruder are 60℃, 120℃, 180℃, 200℃, 200℃, 200℃, 200℃, 200℃, 220℃, the screw speed is 350 rpm, the screw length-to-diameter ratio is 40:1, and the feeding speed is 35 kg / h.

[0130] Table 1 Table 2 The ABS composite materials of the above embodiments and comparative examples were subjected to the following performance tests: (1) Flame retardant performance: ABS composite material was injection molded into standard strips with a thickness of 3.0 mm. The vertical burning flame retardant performance of the strips was tested according to UL94-2023 standard, and the average value of t1+t2 was determined. (2) Appearance quality of the part after painting: The ABS composite material is injected at 220℃ to form a square plate with a gate. The size of the square plate is 200×230×2mm. Paint is sprayed on the surface of the sample and the defects such as spray marks are observed. If there are spray marks, the farthest extension distance of the spray marks on the surface of the part is measured. The measurement reference is the straight distance from the beginning end to the end of the spray mark.

[0131] The test results are shown in Table 3, where “NG” indicates that the V-2 level was not achieved.

[0132] Table 3 As can be seen from the above data, the ABS composite materials in the above embodiments have good flame retardancy, such as the flame retardancy (thickness 3.0mm) reaching V-0 level, and the average value of t1+t2 is less than 5 s; and their parts have a good appearance after painting.

[0133] Comparative Example 1, lacking toughening agent, exhibited defects such as jetting marks after painting; Comparative Example 2, using ABS high-resin powder as toughening agent, also showed defects such as jetting marks after painting.

[0134] Comparative Examples 3 and 4 showed a significant deterioration in the flame retardancy of the composite material due to the absence of hydrocarbon-substituted phosphines or brominated flame retardants, indicating that hydrocarbon-substituted phosphines and brominated flame retardants synergistically improve the flame retardancy of the composite material.

[0135] Comparative Examples 5 and 6 showed a significant deterioration in flame retardancy of the composite material due to the absence of dialkyl-substituted or monoalkyl-substituted phosphinates, indicating that dialkyl-substituted and monoalkyl-substituted phosphinates synergistically improve flame retardancy.

[0136] Comparative Example 7 showed that the flame retardancy of the composite material was significantly deteriorated because other flame retardants were used to replace the monohydrocarbon group that replaced the phosphinate.

[0137] Examples 11-14 These examples all provide an ABS composite material. Their preparation methods differ from those in Example 1 in that the formulations are different, as detailed in Table 4.

[0138] Table 4 Flame retardancy and post-painting appearance quality tests were conducted on Examples 11-14. The test method here differs from the aforementioned test methods in that the composite material was injection molded into a standard strip with a thickness of 1.5 mm for the flame retardancy test. The test results are shown in Table 5.

[0139] Table 5 As shown in Table 5, by adding an appropriate amount of anti-dripping agent, UL-94 V-0 / 1.5mm can be achieved, with the average value of t1+t2 being below 9s. Moreover, the appearance quality of the parts after painting is good, making it suitable for preparing thinner-walled products.

[0140] 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. An ABS composite material, characterized in that, It includes the following components in parts by weight: 50-78.5 parts of ABS resin, 3-15 parts of toughening agent, 3-13 parts of dialkyl-substituted phosphonate, 0.3-2.5 parts of monoalkyl-substituted phosphonate, and 13-20 parts of brominated flame retardant. The toughening agent includes at least one of methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, polymethylsiloxane, and ASA. 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 aryl 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 ABS composite material as described in claim 1, characterized in that, The toughening agent is 4 to 10 parts by weight.

3. The ABS composite material as described in claim 1, characterized in that, At least one of the following conditions must be met: (1) The dialkyl-substituted phosphinates include 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 diisobutylphosphinate. Zinc diphosphonate, zinc di-n-pentylphosphonate, zinc di-isopentylphosphonate, zinc di-n-hexylphosphonate, zinc di-n-heptylphosphonate, zinc di-n-octylphosphonate, zinc diphenylethylphosphonate, magnesium diethylphosphonate, magnesium di-n-propylphosphonate, magnesium di-isopropylphosphonate, magnesium di-n-butylphosphonate, magnesium di-isobutylphosphonate, magnesium di-n-pentylphosphonate, magnesium di-isopentylphosphonate, magnesium di-n-hexylphosphonate, magnesium di-n-heptylphosphonate, magnesium di-n-octylphosphonate, zinc diphenylethylphosphonate Magnesium phosphinate, diethylphosphinate titanium, di-n-propyl titanium phosphinate, diisopropyl titanium phosphinate, di-n-butyl titanium phosphinate, diisobutyl titanium phosphinate, di-n-pentyl titanium phosphinate, diisopentyl titanium phosphinate, di-n-hexyl titanium phosphinate, di-n-heptyl titanium phosphinate, di-n-octyl titanium phosphinate, diphenylethyl titanium phosphinate, calcium diethylphosphinate, di-n-propyl calcium phosphinate, diisopropyl calcium phosphinate, di-n-butyl calcium phosphinate, diisobutyl calcium phosphinate, di-n-pentyl... 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-hexylferric phosphonate, di-n-heptylferric phosphonate, and diphenylethylferric phosphonate; (2) The monoalkyl-substituted phosphinates include aluminum ethyl phosphinate, aluminum n-propyl phosphinate, aluminum isopropyl phosphinate, aluminum n-butyl phosphinate, aluminum isobutyl phosphinate, aluminum n-pentyl phosphinate, aluminum isopentyl phosphinate, aluminum n-hexyl phosphinate, aluminum n-heptyl phosphinate, aluminum n-octyl phosphinate, aluminum cyclohexyl phosphinate, aluminum phenyl phosphinate, aluminum benzyl phosphinate, aluminum phenylethyl phosphinate, zinc ethyl phosphinate, zinc n-propyl phosphinate, zinc isopropyl phosphinate, zinc n-butyl phosphinate, zinc isobutyl phosphinate, and zinc n-pentyl phosphinate. Zinc phosphinate, zinc isopentyl phosphinate, zinc hexyl phosphinate, zinc heptyl phosphinate, zinc octyl phosphinate, zinc cyclohexyl phosphinate, zinc phenyl phosphinate, zinc benzyl phosphinate, zinc phenethyl phosphinate, magnesium ethyl phosphinate, magnesium propyl phosphinate, magnesium isopropyl phosphinate, magnesium butyl phosphinate, magnesium isobutyl phosphinate, magnesium pentyl phosphinate, magnesium isopentyl phosphinate, magnesium hexyl phosphinate, magnesium heptyl phosphinate, magnesium octyl phosphinate, magnesium cyclohexyl phosphinate, magnesium phenyl phosphinate, magnesium benzyl phosphinate, magnesium phenethyl phosphinate Magnesium phosphine, ethyl phosphine, n-propyl titanium phosphine, isopropyl titanium phosphine, n-butyl titanium phosphine, isobutyl titanium phosphine, n-pentyl titanium phosphine, isopentyl titanium phosphine, n-hexyl titanium phosphine, n-heptyl titanium phosphine, n-octyl titanium phosphine, cyclohexyl titanium phosphine, phenyl titanium phosphine, benzyl titanium phosphine, phenylethyl titanium phosphine, calcium ethyl phosphine, calcium n-propyl phosphine, calcium isopropyl phosphine, calcium n-butyl phosphine, calcium isobutyl phosphine, calcium n-pentyl phosphine, calcium isopentyl phosphine. At least one of the following: calcium hexylphosphonate, calcium heptylphosphonate, calcium octylphosphonate, calcium cyclohexylphosphonate, calcium phenylphosphonate, calcium benzylphosphonate, calcium phenylethylphosphonate, ferric ethylphosphonate, ferric propylphosphonate, ferric isopropylphosphonate, ferric butylphosphonate, ferric isobutylphosphonate, ferric pentylphosphonate, ferric isopentylphosphonate, ferric hexylphosphonate, ferric heptylphosphonate, ferric octylphosphonate, ferric cyclohexylphosphonate, ferric phenylphosphonate, ferric benzylphosphonate, and ferric phenylethylphosphonate; (3) The bromine content in the ABS composite material is 8.5%~13% by mass; (4) The brominated flame retardant includes at least one of the following: brominated triazine, brominated epoxy resin, decabromodiphenyl ethane, ethylene bis(tetrabromophthalimide), brominated polystyrene, polybrominated styrene, brominated polycarbonate, and pentabromobenzyl polyacrylate. (5) In the methyl methacrylate-butadiene-styrene copolymer, the weight percentage of methyl methacrylate is 11%~24%, the weight percentage of butadiene is 50%~80%, and the weight percentage of styrene is 9%~26%; (6) In the methyl methacrylate-butadiene-styrene copolymer, the rubber core is at least one of polybutadiene and butadiene-styrene copolymer SBR rubber, and the shell is at least one of methyl methacrylate-styrene copolymer and polymethyl methacrylate; (7) The weight-average molecular weight of the chlorinated polyethylene is 100,000 to 500,000, and the weight percentage of chlorine is 20% to 45%. (8) The polymethylsiloxane has a weight-average molecular weight of 50,000 to 1,000,000 and a silicon content of 10% to 40% by weight. (9) The ASA contains the following monomer units in weight percentage: 0-10% polymethylsiloxane, 50-60% butyl acrylate, 8-13% acrylonitrile, and 27-32% styrene.

4. The ABS composite material as described in claim 1, characterized in that, It also includes an anti-drip agent, wherein the amount of the anti-drip agent is 0.1 to 0.5 parts by weight.

5. The ABS composite material as described in claim 4, characterized in that, 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.

6. The ABS composite material as described in claim 1, characterized in that, The ABS resin includes at least one of a mixture of ABS high-resin powder and SAN resin, and an acrylonitrile-butadiene-styrene terpolymer, wherein the mass ratio of ABS high-resin powder to SAN resin in the mixture is 1.5:8.5 to 3.7:6.

3.

7. The ABS composite material as described in claim 6, characterized in that, At least one of the following conditions must be met: (A) The butadiene content in the ABS high-resin powder is 55%~65% by weight; (B) The melt index of the SAN resin at a temperature of 220°C and a load of 10 kg is 8~95 g / 10 min; the weight percentage of acrylonitrile in the SAN resin is 20%~35%; (C) The melt index of the acrylonitrile-butadiene-styrene terpolymer at a temperature of 220°C and a load of 10 kg is 8~78 g / 10 min; in the acrylonitrile-butadiene-styrene terpolymer, the weight percentage of acrylonitrile is 13%~30%, the weight percentage of butadiene is 6%~30%, and the weight percentage of styrene is 40%~81%.

8. The method for preparing the ABS composite material according to any one of claims 1 to 7, characterized in that, Includes the following steps: The raw materials are mixed and dispersed, melt-extruded, and granulated to obtain ABS composite material.

9. A molded part, characterized in that, It is injection molded from the ABS composite material as described in any one of claims 1 to 7.

10. The molded part as described in claim 9, characterized in that, The surface of the molded part is covered with a paint layer.

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