Flame retardant composition, thermoplastic polymer composite and its application and shaped articles

Abstract

The application discloses a flame retardant composition, a thermoplastic polymer composite and application and a molded part thereof, and belongs to the technical field of flame retardants. The application combines a bromine-based flame retardant, a dihydrocarbyl-substituted phosphinic acid salt and a mono-hydrocarbyl-substituted phosphinic acid salt, controls the respective dosages within a specific range, and makes the prepared flame retardant composition, when applied to a thermoplastic polymer, simultaneously improve the flame retardant performance and high-temperature processing performance of the polymer by virtue of the synergistic effect of the three, so that the thermoplastic polymer can be adapted to application scenarios with high requirements for high-temperature processing conditions and flame retardant effects, such as being suitable for preparing electronic and electrical products.

Description

Technical Field

[0001] This application relates to the field of flame retardant technology, specifically to flame retardant compositions, thermoplastic polymer composites, and their applications and molded parts. Background Technology

[0002] Thermoplastic polymers typically require the addition of flame retardants to improve their flame retardancy. Currently, the mainstream flame retardant compositions include: the classic bromine-antimony blend consisting of brominated flame retardants and antimony-based flame retardants, and the halogen-free phosphorus-nitrogen blend consisting of phosphines and nitrogen-containing flame retardants. Among them, the traditional bromine-antimony compound combination has the widest applicability. For example, patents CN115109350A, CN101463177A, CN114605702A, CN108192221A and CN112795147A all use this composition, but it has obvious shortcomings: the thermal stability of bromine flame retardants is poor, and they are prone to instability during processing, resulting in poor high-temperature processability of the material. Halogen-free phosphorus-nitrogen compound combinations, such as aluminum diethylphosphinate (i.e., ADP, Al((C2H5)2PO2))3) compounded with melamine cyanurate (MCA) and melamine polyphosphate (MPP) respectively, have been disclosed in patent literature such as CN112574535A, CN120699426A and CN114430763A. However, due to the poor thermal stability of MCA and MPP themselves, the overall processing performance of this system is poor. CN110520467A discloses the use of a brominated flame retardant tris(2,4,6-tribromophenoxy)triazine in combination with Al((C2H5)2PO2))3, or with at least one of Al(H2PO2)3 and Ca(H2PO2)2 and Al((C2H5)2PO2))3, to improve the flame retardant properties of resin systems such as ABS and HIPS. However, this system also suffers from poor thermal stability, which can easily lead to unsatisfactory high-temperature processability of the material.

[0003] Therefore, there is an urgent need to develop a flame-retardant system that combines good flame retardancy with high-temperature processing properties. Summary of the Invention

[0004] Based on the deficiencies of the existing technology, the purpose of this application is to provide a flame retardant composition, a thermoplastic polymer composite material, and its application and molded parts, wherein the flame retardant composition has both good flame retardancy and high-temperature processability.

[0005] To achieve the above objectives, in a first aspect, this application provides a flame retardant composition comprising the following components in parts by weight: 83-97 parts of dialkyl-substituted phosphinate, 3-17 parts of monoalkyl-substituted phosphinate, and 150-360 parts of brominated flame retardant. 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.

[0006] By controlling the amounts of the aforementioned brominated flame retardant, dialkyl-substituted phosphinate, and monoalkyl-substituted phosphinate within the specific ranges described above, the resulting flame retardant composition, when applied to thermoplastic polymers, can enhance both the flame retardant properties and high-temperature processing performance of the polymers through the synergistic effect of the three components. This enables the thermoplastic polymers to be suitable for application scenarios that require both high-temperature processing conditions and high flame retardant performance.

[0007] The dialkyl-substituted phosphonate is 83 to 97 parts by weight, such as 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, or any two of the above ranges.

[0008] The monoalkyl-substituted phosphonate is 3 to 17 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, 16 parts by weight, 17 parts by weight, or any two of the above ranges.

[0009] The brominated flame retardant is present in a range of 150-360 parts by weight, such as 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, 200 parts by weight, 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, 290 parts by weight, 300 parts by weight, 310 parts by weight, 320 parts by weight, 330 parts by weight, 340 parts by weight, 350 parts by weight, 360 parts by weight, or any two of the above ranges. Preferably, the brominated flame retardant constitutes more than 55% of the weight in the flame retardant composition, such as 55%, 57%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 78.3%, or any two of the above ranges.

[0010] 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.

[0011] 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.

[0012] 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-.

[0013] For example, the C3 to C8 cycloalkyl group is at least one of C3, C4, C5, C6, C7 or C8 cycloalkyl groups.

[0014] 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.

[0015] For example, aromatic groups include, but are not limited to, phenyl groups.

[0016] For example, n is selected from 2, 3 or 4.

[0017] For example, m is selected from 2, 3 or 4.

[0018] 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.

[0019] The weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is (4.88~32.33):1, such as 4.88:1, 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, 32.33:1 or any two of the above ranges.

[0020] Preferably, the weight ratio of the dialkyl-substituted phosphinate to the monoalkyl-substituted phosphinate is (9~19):1. When the weight ratio is within this range, the temperature at which they promote the decomposition of brominated flame retardants is more suitable, thereby enabling the flame retardant composition to better improve the flame retardancy and high-temperature processability of thermoplastic polymers.

[0021] Preferably, the weight ratio of the brominated flame retardant to the total weight of the dialkyl-substituted phosphinate and the monoalkyl-substituted phosphinate is (1.5~3.6):1, such as 1.5:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.3:1, 3.6:1, or any range formed by two or more of the above. More preferably, the weight ratio of the brominated flame retardant to the total weight of the dialkyl-substituted phosphinate and the monoalkyl-substituted phosphinate is (1.8~3):1.

[0022] When the weight ratio of the brominated flame retardant to the total weight of the dialkyl-substituted phosphinate and the monoalkyl-substituted phosphinate is in the range of (1.5~3.6):1, especially in the range of (1.8~3):1, the temperature at which the two alkyl-substituted phosphinates promote the decomposition of the brominated flame retardant is more suitable, thereby enabling the flame retardant composition to better improve the flame retardancy and high-temperature processability of the thermoplastic polymer.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] In Formula III, R 1 and R 2 They can be the same, yet they can also be different.

[0028] 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.

[0029] 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-.

[0030] 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.

[0031] 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.

[0032] In Equation III, when R 1 and / or R 2 When selected from aromatic groups, the aromatic group can be phenyl.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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-.

[0037] 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.

[0038] 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.

[0039] In Equation IV, when R 3 When selected from aromatic groups, the aromatic group can be phenyl.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] In one embodiment, the molar ratio of di(or mono)alkyl-substituted sodium hypophosphite to the water-soluble salt is (0.5~8):1.

[0044] 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.

[0045] 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%.

[0046] In one embodiment, the metathesis reaction is carried out under an inert atmosphere. The inert atmosphere may be nitrogen or / or argon.

[0047] 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.

[0048] 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).

[0049] Preferably, the mass percentage of bromine in the flame retardant composition is 30% to 65%, such as 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 63%, or 65%. The mass percentage of bromine in the flame retardant composition (%) = the mass percentage of brominated flame retardant in the flame retardant composition (%) × the mass content of bromine in the brominated flame retardant. For example, the mass content of bromine in commercially available ICL-IP FR-245 and F-3014 is 0.67% (67%) and 0.6% (60%), respectively. To achieve a bromine mass percentage of 40% in the flame retardant composition, the mass percentage of FR-245 in the flame retardant composition needs to be controlled at 59.7%, or the mass percentage of F-3014 in the flame retardant composition needs to be controlled at 66.7%.

[0050] 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%.

[0051] 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.

[0052] Preferably, the brominated flame retardant includes at least one selected from brominated triazine, brominated epoxy resin, decabromodiphenyl ethane, brominated polystyrene, polybrominated styrene, brominated polycarbonate, pentabromobenzyl polyacrylate, and ethylene bis(tetrabromophthalimide). More preferably, the brominated flame retardant includes at least one selected from brominated triazine, ethylene bis(tetrabromophthalimide), and brominated polystyrene to improve flame retardancy and high-temperature processing performance.

[0053] 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.

[0054] In some embodiments, the weight-average molecular weight of the brominated epoxy resin is 700-3000, such as the range formed by any two of 700, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 3000 or above.

[0055] In some embodiments, the weight-average molecular weight of the brominated polystyrene is 3000-8000, such as the range formed by any two of the following: 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000 or above.

[0056] In some embodiments, the weight-average molecular weight of the polybrominated styrene is 3000-8000, such as the range formed by any two of the following: 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000 or more.

[0057] In some embodiments, the weight-average molecular weight of the brominated polycarbonate is 3500-8500, such as the range formed by any two of the following: 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500.

[0058] In some embodiments, the weight-average molecular weight of the polypentabromobenzyl acrylate is 500,000-700,000, 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.

[0059] 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).

[0060] In some embodiments, the flame retardant composition further includes an anti-dripping agent, wherein the anti-dripping agent is present in an amount of 0 to 10 parts by weight. In one embodiment, the anti-dripping agent is present in an amount of 1 to 10 parts by weight to improve anti-dripping performance, which is beneficial for achieving thin-walled UL-94 V-0.

[0061] 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.

[0062] In some embodiments, the flame retardant composition is prepared by mixing and dispersing the component raw materials to obtain the flame retardant composition.

[0063] Secondly, this application provides a thermoplastic polymer composite material including the flame retardant composition.

[0064] For example, the thermoplastic polymer includes at least one selected from acrylonitrile-butadiene-styrene copolymer (ABS), high-impact polystyrene (HIPS), polyamide (PA), polybutylene terephthalate (PBT), acrylonitrile-styrene copolymer (i.e., SAN, AS), and polyolefins. For example, the polyolefin includes, but is not limited to, at least one selected from polyethylene and polypropylene. For example, the polyamide includes, but is not limited to, aliphatic polyamides. For example, the aliphatic polyamide includes, but is not limited to, at least one selected from PA6, PA56, PA66, PA610, and PA1010.

[0065] In some embodiments, the thermoplastic polymer composite material comprises the following components in parts by weight: 74-80 parts of thermoplastic polymer and 20-26 parts of the flame retardant composition; The thermoplastic polymer includes at least one of acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and high-impact polystyrene.

[0066] By controlling the specific amounts of thermoplastic polymer and flame retardant composition contained in the thermoplastic polymer composite material, it can possess both excellent flame retardancy and high-temperature processing performance.

[0067] For example, the thermoplastic polymer is in the range of any two of 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, or more.

[0068] For example, the flame retardant composition is within the range of any two of 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, or more.

[0069] In some embodiments, the acrylonitrile-butadiene-styrene copolymer has a melt index of 6~80g / 10min at a temperature of 220°C and a load of 10kg, and in the acrylonitrile-butadiene-styrene copolymer, the weight percentage of acrylonitrile is 12%~35%, the weight percentage of butadiene is 8%~35%, and the weight percentage of styrene is 30%~80%.

[0070] In some embodiments, the acrylonitrile-butadiene-styrene copolymer has a core-shell structure and / or an island-like structure. The acrylonitrile-butadiene-styrene copolymer can be prepared by bulk polymerization or by emulsion polymerization. It can also be commercially available by blending emulsion-grafted butadiene-grafted SAN copolymer with SAN resin.

[0071] In some embodiments, the melt index of the acrylonitrile-styrene copolymer is 6~100g / 10min at a temperature of 220°C and a load of 10kg, and the weight percentage of acrylonitrile in the acrylonitrile-styrene copolymer is 18~35%.

[0072] In some embodiments, the thermoplastic polymer includes acrylonitrile-butadiene-styrene copolymer high-rubber powder and acrylonitrile-styrene copolymer, wherein the weight ratio of acrylonitrile-butadiene-styrene copolymer high-rubber powder to acrylonitrile-styrene copolymer is 2:8 to 4:6. Specifically, the butadiene weight percentage in the acrylonitrile-butadiene-styrene copolymer high-rubber powder can be selected as 55% to 70%; the acrylonitrile-styrene copolymer can be selected to meet the following conditions: melt index of 6 to 100 g / 10 min at 220°C and 10 kg load, and acrylonitrile weight percentage of 18% to 35%.

[0073] In some embodiments, the high-impact polystyrene has a melt index of 2~15 / 10min at a temperature of 200°C and a load of 5kg, and the butadiene in the high-impact polystyrene accounts for 8%~18% by weight.

[0074] The weight percentage of monomer units in acrylonitrile-butadiene-styrene copolymer and acrylonitrile-butadiene-styrene copolymer high-rubber powder was determined by elemental analysis combined with infrared spectroscopy.

[0075] The weight percentage of monomer units in the acrylonitrile-styrene copolymer was determined by elemental analysis.

[0076] The weight percentage of monomer units in high-impact polystyrene was determined by infrared spectroscopy.

[0077] The melt index of the acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer and high-impact polystyrene was measured according to GB / T 3682-2000.

[0078] Other additives may be added to the thermoplastic polymer composite material as needed to improve the composition's 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.

[0079] 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.

[0080] 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).

[0081] 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.

[0082] 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.

[0083] 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%).

[0084] 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.

[0085] 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.

[0086] 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.

[0087] In some embodiments, the other adjuvants are 0 to 2 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, or any range formed by two or more of these.

[0088] In some embodiments, the thermoplastic polymer is present in the thermoplastic polymer composite material at a weight percentage of 74% or more, such as within the range of any two of 74%, 76%, 78%, 80%, 82%, 84%, 83.3% or more.

[0089] In some embodiments, the flame retardant composition is present in the thermoplastic polymer composite material at a weight percentage of 15% or more, such as within the range of any two of 15%, 16%, 17%, 18%, 19%, 20%, 20.6% or more.

[0090] In some embodiments, the mass percentage of bromine in the thermoplastic polymer composite material is 8% to 13%, such as the range formed by any two of 8%, 9%, 10%, 11%, 12%, or 13%.

[0091] In some embodiments, the preparation method of the thermoplastic polymer composite material includes the following steps: mixing and dispersing the component raw materials, melt extruding, granulating, and obtaining the thermoplastic polymer composite material.

[0092] In one embodiment, melt extrusion and granulation are carried out in a twin-screw extruder when preparing the thermoplastic polymer composite material.

[0093] 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.

[0094] Thirdly, this application provides the application of the aforementioned thermoplastic polymer composite material in the field of electronics and electrical engineering, which can be used to prepare housings and components for household appliances, housings and components for OA equipment (office automation equipment), protective covers for PCB boards (printed circuit boards), housings for backup power supplies, housings for storage batteries, housings for power strips, etc.

[0095] Fourthly, this application provides a molded part formed from the aforementioned thermoplastic polymer composite material. The molding method can be selected with reference to existing technologies, such as including but not limited to injection molding, extrusion molding, blow molding, rotational molding, and / or compression molding.

[0096] Compared with the prior art, the beneficial effects of this application are as follows: This application combines brominated flame retardants, specific types of dialkyl-substituted phosphinates and specific types of monoalkyl-substituted phosphinates, and controls the amount of each within a specific range, so that when the resulting flame retardant composition is applied to thermoplastic polymers, the flame retardant properties and high-temperature processing properties of the polymer are improved by the synergistic effect of the three, thereby enabling the thermoplastic polymer to be suitable for application scenarios with high requirements for high-temperature processing conditions and flame retardant effects, such as the manufacture of electronic and electrical products. Detailed Implementation

[0097] 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.

[0098] 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.

[0099] 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).

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] Monoalkyl-substituted phosphinate 3: Aluminum phenylphosphinate, Hubei Chuyuebang New Material Technology Co., Ltd.

[0105] 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.

[0106] Hypophosphite: Al(H2PO2)3, Fujian Xin'an Technology Co., Ltd., FR605.

[0107] Melamine cyanurate (MCA): Jinan Jinyingtai Chemical Co., Ltd.

[0108] Melamine polyphosphate (MPP): Jinan Jinyingtai Chemical Co., Ltd.

[0109] Brominated flame retardant 1: Bromotriazine, FR-245, ICL-IP.

[0110] Brominated flame retardant 2: Brominated epoxy resin, F-3014, ICL-IP.

[0111] Bromine-based flame retardant 3: Brominated polystyrene, SR-3010, Shandong Xurui New Material Co., Ltd.

[0112] Brominated flame retardant 4: Poly(pentabromobenzyl) acrylate, FR-1025, ICL-IP.

[0113] Brominated flame retardant 5: Ethylene bis(tetrabromophthalimide), BT-93, Albemarle, USA.

[0114] Anti-dripping agent 1: Styrene-acrylonitrile random copolymer coated with polytetrafluoroethylene, Guangzhou Entropy Energy Innovation Materials Co., Ltd., brand name SN80-SA7.

[0115] Anti-dripping agent 2: Styrene-methyl methacrylate copolymer coated polytetrafluoroethylene, Shanghai Puxin Polymer Materials Co., Ltd., grade DB109.

[0116] ABS Resin 1: Emulsion method, Ningbo LG Yongxing Chemical Co., Ltd., HI-121H.

[0117] ABS Resin 2: Bulk method, DOW, grade ABS 8434.

[0118] ABS / SAN: ABS (INEOS Styrolution MAG 50) and SAN (Kumho Chemical Co., Ltd. 310 NTR) were mixed and dispersed at a weight ratio of 3:7.

[0119] HIPS resin: Guoheng Chemical Co., Ltd., PS-350K.

[0120] SAN resin: Liaoning Kingfa Science & Technology Co., Ltd., KFA-130.

[0121] PBT resin: Chang Chun Group, Taiwan, China, PBT 1200-211M.

[0122] PA resin: PA6, Haiyang Technology Co., Ltd., PA6 HY-2500A.

[0123] Polyolefin: Polypropylene, CNOOC Shell Petrochemicals Co., Ltd., PP HP500N.

[0124] 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.

[0125] The formulations of flame retardant compositions 1-25 are shown in Tables 1-2. Their preparation methods include the following steps: mixing and dispersing the raw materials of each component to obtain the flame retardant composition.

[0126] Table 1 Table 2 Examples 1-14 and Comparative Examples 1-7 These examples and comparative examples all provide a thermoplastic polymer composite material, and their preparation methods include the following steps: According to the formulations of thermoplastic polymer composite materials in Tables 3 and 4, the raw materials of each component are mixed and dispersed, fed into a twin-screw extruder for melt extrusion and granulation to obtain thermoplastic polymer composite materials. The twin-screw temperatures in the twin-screw extruder are 60℃, 140℃, 200℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 240℃, the screw speed is 350 rpm, the screw length-to-diameter ratio is 40:1, and the feeding speed is 35 kg / h.

[0127] Table 3 Table 4 The thermoplastic polymer composites of the above embodiments and comparative examples were subjected to the following performance tests: (1) Flame retardant performance: The thermoplastic polymer composite material was injection molded into a standard sample with a thickness of 3.0 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) High temperature processing stability: The thermoplastic polymer composite material was injection molded at 240℃ without retention or with retention for 10 min to make a sample of ISO 527-2-2025 Type 1BA specification. The tensile strength at 25℃ was tested according to the standard ISO 527-2-2025. The tensile strength retention rate was calculated according to the following formula: Tensile strength retention rate = tensile strength of sample with retention for 10 min / tensile strength of sample without retention × 100%.

[0128] The test results are shown in Table 5, where “NG” indicates that the V-2 level was not achieved.

[0129] Table 5 As can be seen from the above data, the thermoplastic polymer composite materials in the above embodiments have both excellent flame retardancy and high-temperature processing stability. For example, the flame retardancy (thickness 3.0 mm) reaches V-0 level, the average value of t1+t2 is below 9.5 s, and the tensile strength retention rate is above 90%, making them suitable for manufacturing battery casings, etc.

[0130] Comparative Examples 1 and 2, lacking either dialkyl-substituted or monoalkyl-substituted phosphines, exhibited significantly deteriorated flame retardancy and high-temperature processing stability in their thermoplastic polymer composites. This indicates that dialkyl-substituted and monoalkyl-substituted phosphines synergistically improve flame retardancy and high-temperature processing stability.

[0131] Comparative Examples 3 and 4, lacking substituted phosphines or brominated flame retardants, showed significant deterioration in the flame retardancy and high-temperature processing stability of the thermoplastic polymer composites. This indicates that substituted phosphines and brominated flame retardants synergistically improve the flame retardancy and high-temperature processing stability of the thermoplastic polymer composites.

[0132] Comparative Examples 5-7 showed that the flame retardancy and / or high-temperature processing stability of thermoplastic polymer composites were significantly deteriorated due to the use of other flame retardants to replace monohydrophosphinates.

[0133] A comparison of Examples 1-4 shows that when the weight ratio of dialkyl-substituted phosphonates to monoalkyl-substituted phosphonates is in the range of (9-19):1, the thermoplastic polymer composite material exhibits superior flame retardancy and high-temperature processing stability.

[0134] As can be seen from the comparison of Examples 1 and 5-7, when the weight ratio of the brominated flame retardant to the total weight of dialkyl-substituted phosphines and monoalkyl-substituted phosphines is in the range of (1.8~3):1, the thermoplastic polymer composite material exhibits better flame retardancy and high-temperature processing stability.

[0135] Examples 15-20 These embodiments all provide a thermoplastic polymer composite material. Their preparation methods differ from those in Example 1 in that the formulations are different, as detailed in Table 6.

[0136] Table 6 Flame retardancy and high-temperature processing performance were tested for Examples 15-20. The test method here differs from the previous test methods in that the thermoplastic polymer composite material was injection molded into a standard specimen with a thickness of 1.5 mm for the flame retardancy test. The test results are shown in Table 7.

[0137] Table 7 As shown in Table 7, by adding an appropriate amount of anti-dripping agent to the flame retardant composition, UL-94 V-0 / 1.5mm can be achieved, with the average value of t1+t2 below 8.9 s. Moreover, the tensile strength retention rate of the thermoplastic polymer composite material is also above 90%, and it has good high-temperature processing performance, making it suitable for preparing thinner-walled products, such as PCB board protective covers.

[0138] Examples 21-23 These embodiments all provide a thermoplastic polymer composite material. Their preparation methods differ from those in Example 1 in that the formulations are different, as detailed in Table 8.

[0139] Table 8 Flame retardancy tests were conducted on Examples 21-23. The test method here differed from the previous test methods in that the thermoplastic polymer composite material was injection molded into a standard strip with a thickness of 1.5 mm for the flame retardancy performance test. The test results are shown in Table 9.

[0140] Table 9 As shown in Table 9, the thermoplastic polymer composites of Examples 21-23 have good flame retardancy and can achieve UL-94 V-0 / 1.5mm, with an average t1+t2 value of less than 5.7 s.

[0141] 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 flame retardant composition characterized in that, It includes the following components in parts by weight: 83-97 parts of dialkyl-substituted phosphinate, 3-17 parts of monoalkyl-substituted phosphinate, and 150-360 parts of brominated flame retardant; 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. ， wherein R 1 , R 2 and R 3 are each independently selected from the group consisting of C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C7-C8 aralkyl, aryl; 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 flame retardant composition of claim 1, wherein The weight ratio of the dialkyl-substituted phosphonate to the monoalkyl-substituted phosphonate is (9~19):

1.

3. The flame retardant composition of claim 1, wherein The weight ratio of the brominated flame retardant to the total weight of the dialkyl-substituted phosphonate and the monoalkyl-substituted phosphonate is (1.5~3.6):

1.

4. The flame retardant composition of claim 3, wherein The weight ratio of the brominated flame retardant to the total weight of the dialkyl-substituted phosphonate and the monoalkyl-substituted phosphonate is (1.8~3):

1.

5. The flame retardant composition according to claim 1, characterized in that, At least one of the following conditions must be met: (A1) 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 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-hexylferric phosphonate, di-n-heptylferric phosphonate, and diphenylethylferric phosphonate; (A2) The monoalkyl-substituted phosphines include aluminum ethylphosphines, aluminum n-propylphosphines, aluminum isopropylphosphines, aluminum n-butylphosphines, aluminum isobutylphosphines, aluminum n-pentylphosphines, aluminum isopentylphosphines, aluminum n-hexylphosphines, aluminum n-heptylphosphines, aluminum n-octylphosphines, aluminum cyclohexylphosphines, aluminum phenylphosphines, aluminum benzylphosphines, aluminum phenylethylphosphines, zinc ethylphosphines, zinc n-propylphosphines, zinc isopropylphosphines, zinc n-butylphosphines, zinc isobutylphosphines, zinc n-pentylphosphines, and aluminum phenylphosphines. 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 hexyl phosphinate, calcium heptyl phosphinate, calcium octyl phosphinate, calcium cyclohexyl phosphinate, calcium phenyl phosphinate, calcium benzyl phosphinate, calcium phenylethyl phosphinate, ferric ethyl phosphinate, ferric propyl phosphinate, ferric isopropyl phosphinate, ferric butyl phosphinate, ferric isobutyl phosphinate, ferric pentyl phosphinate, ferric isopentyl phosphinate, ferric hexyl phosphinate, ferric heptyl phosphinate, ferric octyl phosphinate, ferric cyclohexyl phosphinate, ferric phenyl phosphinate, ferric benzyl phosphinate, and ferric phenylethyl phosphinate; (A3) The bromine content in the flame retardant composition is 30%~65% by mass; (A4) The brominated flame retardant includes at least one of the following: brominated triazine, brominated epoxy resin, decabromodiphenyl ethane, brominated polystyrene, polybrominated styrene, brominated polycarbonate, pentabromobenzyl polyacrylate, and ethylene bis(tetrabromophthalimide).

6. The flame retardant composition according to claim 1, characterized in that, It also includes an anti-drip agent, wherein the amount of the anti-drip agent is 1 to 10 parts by weight.

7. The flame retardant composition according to claim 6, 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.

8. A thermoplastic polymer composite material, characterized in that, The flame retardant composition includes any one of claims 1 to 7.

9. The thermoplastic polymer composite material according to claim 8, characterized in that, The thermoplastic polymer in the thermoplastic polymer composite material includes at least one of acrylonitrile-butadiene-styrene copolymer, high-impact polystyrene, polyamide, polybutylene terephthalate, acrylonitrile-styrene copolymer, and polyolefin.

10. The thermoplastic polymer composite material according to claim 9, characterized in that, It comprises the following components in parts by weight: 74-80 parts of thermoplastic polymer, and 20-26 parts of the flame retardant composition; The thermoplastic polymer includes at least one of acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and high-impact polystyrene.

11. The thermoplastic polymer composite material according to claim 10, characterized in that, At least one of the following conditions must be met: (B1) The melt index of the acrylonitrile-butadiene-styrene copolymer at a temperature of 220°C and a load of 10 kg is 6~80 g / 10 min, and in the acrylonitrile-butadiene-styrene copolymer, the weight percentage of acrylonitrile is 12%~35%, the weight percentage of butadiene is 8%~35%, and the weight percentage of styrene is 30%~80%; (B2) The melt index of the acrylonitrile-styrene copolymer at a temperature of 220°C and a load of 10 kg is 6~100 g / 10 min, and the weight percentage of acrylonitrile in the acrylonitrile-styrene copolymer is 18~35%; (B3) The thermoplastic polymer includes acrylonitrile-butadiene-styrene copolymer high-rubber powder and acrylonitrile-styrene copolymer, wherein the weight ratio of acrylonitrile-butadiene-styrene copolymer high-rubber powder to acrylonitrile-styrene copolymer is 2:8 to 4:6; (B4) The melt index of the high-impact polystyrene under the conditions of 200℃ and 5kg load is 2~15g / 10min, and the weight ratio of butadiene in the high-impact polystyrene is 8%~18%.

12. The application of the thermoplastic polymer composite material as described in any one of claims 8 to 11 in the field of electronics and electrical engineering.

13. A molded part, characterized in that, It is formed from the thermoplastic polymer composite material as described in any one of claims 8 to 11.

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