Flame retardant composition, resin composite and its application and molded part

Abstract

The application discloses a flame retardant composition, a resin composite material and application and a molded part thereof, and belongs to the technical field of flame retardants. The application combines dihydrocarbyl-substituted phosphinate, mono-hydrocarbyl-substituted phosphinate and mono-hydrocarbyl-substituted phosphonate according to specific amounts, controls the dihydrocarbyl-substituted phosphinate to contain a specific amount of dihydrocarbyl-substituted phosphinate with a tertiary carbon structure, so that the prepared flame retardant composition can improve the flame retardant performance of a material and reduce mold fouling in a processing process when being applied to a resin, and is 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, resin composite materials, and their applications and molded parts. Background Technology

[0002] Dialkyl-substituted phosphines, especially aluminum diethylphosphines, have been widely used as flame retardants in modified plastic systems such as polyamides and polyesters. However, existing dialkylphosphines generally have high decomposition temperatures, resulting in limited flame retardant efficiency in resin systems with lower decomposition temperatures, such as polyethylene, polypropylene, high-impact polystyrene (HIPS), and acrylonitrile-butadiene-styrene polymers (ABS). For example, adding up to 30 wt% aluminum diethylphosphines to ABS resin systems only achieves a UL94 3.0 mm V-1 flame retardant rating. Furthermore, dialkyl-substituted phosphines are prone to sublimation during processing, forming mold deposits.

[0003] CN105940085A discloses a halogen-free flame retardant mixture comprising 1 to 99 wt% component A and 1 to 99 wt% component B. Component A comprises 85 to 99.995 wt% of metallic Mg, Ca, Al, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or protonated nitrogen-containing base solid diethylphosphine salts and 0.005 to 15 wt% of non-flammable additives, and component B is aluminum phosphite. This halogen-free flame retardant mixture exhibits uniform free flowability and can achieve good flame retardant effects; however, it generates significant scale buildup during high-temperature processing, making it difficult to meet practical application requirements.

[0004] Therefore, there is an urgent need to optimize the dialkyl-substituted phosphonate flame retardant system. Summary of the Invention

[0005] Based on the deficiencies of the existing technology, the purpose of this application is to provide a flame retardant composition, a resin composite material, and its application and molding parts, wherein the flame retardant composition not only has good flame retardancy, but also produces less mold residue during processing.

[0006] To achieve the above objectives, in a first aspect, this application provides a flame retardant composition comprising the following components in parts by weight: 75-95 parts of dialkyl-substituted phosphonates, 4.7-20 parts of monoalkyl-substituted phosphonates, and 0.1-5 parts of monoalkyl-substituted phosphonates; The dialkyl-substituted phosphonate is at least one of the compounds of formula I, the monoalkyl-substituted phosphonate is at least one of the compounds of formula II, and the monoalkyl-substituted phosphonate is at least one of the compounds of formula A. , Among them, R 1 R 2 R 3 and R 4 Each group is independently selected from the following groups: C4-C8 straight-chain alkyl, C4-C8 branched alkyl, C4-C8 cycloalkyl, C7-C8 aralkyl, and aromatic group; X, Y, and Z are each independently selected from Al, Mg, Ca, Zn, Ti, or Fe; n, m, and a are each independently selected from integers between 2 and 4; The dialkyl-substituted phosphonate comprises a dialkyl-substituted phosphonate having a tertiary carbon structure; the dialkyl-substituted phosphonate having a tertiary carbon structure is 0.08 to 7 parts by weight.

[0007] By compounding dialkyl-substituted phosphonates with monoalkyl-substituted phosphonates and monoalkyl-substituted phosphonates in specific amounts, and controlling the dialkyl-substituted phosphonates to contain a specific amount of dialkyl-substituted phosphonates with tertiary carbon structures, it is possible to simultaneously improve flame retardancy and reduce mold fouling.

[0008] The dialkyl-substituted phosphinate is present in a range of 75-95 parts by weight, such as 75 parts by weight, 776 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 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, or any two of the above. Preferably, the dialkyl-substituted phosphinate in the flame retardant composition comprises more than 70% by weight, such as 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, or any two of the above.

[0009] The monoalkyl-substituted phosphonate is 4.7 to 20 parts by weight, such as 4.7 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, 18 parts by weight, 19 parts by weight, 20 parts by weight, or any two of the above ranges.

[0010] The monoalkyl-substituted phosphonate is 0.1 to 5 parts by weight, such as 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, or any two of the above ranges.

[0011] The dialkyl-substituted phosphonate having a tertiary carbon structure is in the range of 0.08 to 7 parts by weight, such as 0.08 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, or any two of the above ranges.

[0012] In Equations I, II, and A, R 1 R 2 R 3 and R 4 They can be completely different, or two, three, or four of them can be the same; X, Y, and Z can be the same, or two or three of them can be different; n, m, and a can be the same, or two or three of them can be different.

[0013] For example, the C4-C8 straight-chain alkyl group is at least one of C4, C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0014] For example, the C4-C8 branched alkyl group is at least one of C4, C5, C6, C7, or C8 branched alkyl groups. In some embodiments, the C4-C8 branched alkyl group is at least one of (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-.

[0015] For example, the C4 to C8 cycloalkyl group is at least one of C4, C5, C6, C7 or C8 cycloalkyl groups.

[0016] 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.

[0017] For example, aromatic groups include, but are not limited to, phenyl groups.

[0018] For example, n is selected from 2, 3 or 4.

[0019] For example, m is selected from 2, 3 or 4.

[0020] For example, 'a' is selected from 2, 3, or 4.

[0021] Preferably, R 1 R 2 R 3 and R 4 Each group is independently selected from the following groups: C4~C8 straight-chain alkyl, C4~C8 branched alkyl, and C7~C8 aralkyl, which not only have excellent stability but are also easy to synthesize.

[0022] Preferably, the dialkyl-substituted phosphinate with a tertiary carbon structure includes aluminum bis(1,1-dimethylethyl)phosphinate, aluminum bis(2-methylpropyl)phosphinate, aluminum butyl(2-methylpropyl)phosphinate, aluminum bis(2,4,4-trimethylpentyl)phosphinate, aluminum bis(2-ethylhexyl)phosphinate, aluminum bis(3,3-dimethylbutyl)phosphinate, zinc bis(1,1-dimethylethyl)phosphinate, and zinc bis(2-methylpropyl)phosphinate. Butyl(2-methylpropyl)zinc phosphinate, bis(2,4,4-trimethylpentyl)zinc phosphinate, bis(2-ethylhexyl)zinc phosphinate, bis(3,3-dimethylbutyl)zinc phosphinate, bis(1,1-dimethylethyl)magnesium phosphinate, bis(2-methylpropyl)magnesium phosphinate, butyl(2-methylpropyl)magnesium phosphinate, bis(2,4,4-trimethylpentyl)magnesium phosphinate, bis(2-ethylhexyl)magnesium phosphinate, bis(3,3-dimethyl)butyl)zinc phosphinate Butyl(2-methylpropyl) phosphine magnesium, bis(1,1-dimethylethyl) phosphine titanium, bis(2-methylpropyl) phosphine titanium, butyl(2-methylpropyl) phosphine titanium, bis(2,4,4-trimethylpentyl) phosphine titanium, bis(2-ethylhexyl) phosphine titanium, bis(3,3-dimethylbutyl) phosphine titanium, bis(1,1-dimethylethyl) phosphine calcium, bis(2-methylpropyl) phosphine calcium, butyl(2-methylpropyl) phosphine calcium, At least one of bis(2,4,4-trimethylpentyl)phosphonic acid calcium, bis(2-ethylhexyl)phosphonic acid calcium, bis(3,3-dimethylbutyl)phosphonic acid calcium, bis(1,1-dimethylethyl)phosphonic acid iron, bis(2-methylpropyl)phosphonic acid iron, butyl(2-methylpropyl)phosphonic acid iron, bis(2,4,4-trimethylpentyl)phosphonic acid iron, bis(2-ethylhexyl)phosphonic acid iron, and bis(3,3-dimethylbutyl)phosphonic acid iron.

[0023] Preferably, the dialkyl-substituted phosphinates include 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 di-n-butylphosphinate, zinc diisobutylphosphinate, zinc di-n-pentylphosphinate, zinc diisopentylphosphinate, zinc di-n-hexylphosphinate, zinc di-n-heptylphosphinate, zinc di-n-octylphosphinate, zinc diphenylethylphosphinate, magnesium di-n-butylphosphinate, magnesium diisobutylphosphinate, magnesium di-n-pentylphosphinate, magnesium diisopentylphosphinate, magnesium di-n-hexylphosphinate, magnesium di-n-heptylphosphinate, magnesium di-n-octylphosphinate, and aluminum diphenylethylphosphinate. The following is a list of at least one of magnesium diphosphonate, di-n-butylphosphonate, diisobutylphosphonate, di-n-pentylphosphonate, diisopentylphosphonate, di-n-hexylphosphonate, di-n-heptylphosphonate, di-n-octylphosphonate, diphenylethylphosphonate, calcium di-n-butylphosphonate, calcium diisobutylphosphonate, calcium di-n-pentylphosphonate, calcium diisopentylphosphonate, calcium di-n-hexylphosphonate, calcium di-heptylphosphonate, calcium di-octylphosphonate, calcium diphenylethylphosphonate, iron di-n-butylphosphonate, iron diisobutylphosphonate, iron di-n-pentylphosphonate, iron diisopentylphosphonate, iron di-hexylphosphonate, iron di-heptylphosphonate, iron di-octylphosphonate, and iron diphenylethylphosphonate.

[0024] Preferably, the monoalkyl-substituted phosphinate includes aluminum n-butylphosphinate, aluminum isobutylphosphinate, aluminum n-pentylphosphinate, aluminum isopentylphosphinate, aluminum n-hexylphosphinate, aluminum n-heptylphosphinate, aluminum n-octylphosphinate, aluminum cyclohexylphosphinate, aluminum phenylphosphinate, aluminum benzylphosphinate, aluminum phenethylphosphinate, zinc n-butylphosphinate, zinc isobutylphosphinate, zinc n-pentylphosphinate, and zinc isopentylphosphinate. Zinc hexyl phosphinate, zinc heptyl phosphinate, zinc octyl phosphinate, zinc cyclohexyl phosphinate, zinc phenyl phosphinate, zinc benzyl phosphinate, zinc phenethyl 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 phenyl phosphinate, magnesium phenethyl phosphinate, magnesium phenyl phosphinate, magnesium phenyl phosphinate, magnesium phenyl phosphinate, magnesium phenyl phosphinate, magnesium cyclohexyl ... Magnesium phosphinate, butyl titanium phosphinate, isobutyl titanium phosphinate, pentyl titanium phosphinate, isopentyl titanium phosphinate, hexyl titanium phosphinate, heptyl titanium phosphinate, octyl titanium phosphinate, cyclohexyl titanium phosphinate, phenyl titanium phosphinate, benzyl titanium phosphinate, phenethyl titanium phosphinate, calcium butyl phosphinate, isobutyl calcium phosphinate, pentyl calcium phosphinate, isopentyl calcium phosphinate, hexyl calcium phosphinate, heptyl At least one of the following: calcium phosphite, octyl calcium phosphite, cyclohexyl calcium phosphite, phenyl calcium phosphite, benzyl calcium phosphite, phenylethyl calcium phosphite, ferric butyl phosphite, ferric isobutyl phosphite, ferric pentyl phosphite, ferric isopentyl phosphite, ferric phenyl phosphite, ferric phenyl benzyl phosphite, and ferric phenylethyl phosphite.

[0025] Preferably, the monoalkyl-substituted phosphonate includes aluminum n-butylphosphonate, aluminum isobutylphosphonate, aluminum n-pentylphosphonate, aluminum isopentylphosphonate, aluminum n-hexylphosphonate, aluminum isohexylphosphonate, aluminum n-heptylphosphonate, aluminum isoheptylphosphonate, aluminum n-octylphosphonate, aluminum isooctylphosphonate, aluminum cyclohexylphosphonate, aluminum phenylphosphonate, aluminum benzylphosphonate, aluminum phenethylphosphonate, zinc n-butylphosphonate, zinc isobutylphosphonate, zinc n-pentylphosphonate, zinc isopentylphosphonate, zinc n-hexylphosphonate, and aluminum isohexylphosphonate. Zinc phosphonate, zinc n-heptylphosphonate, zinc isoheptylphosphonate, zinc n-octylphosphonate, zinc isooctylphosphonate, zinc cyclohexylphosphonate, zinc phenylphosphonate, zinc benzylphosphonate, zinc phenethylphosphonate, magnesium n-butylphosphonate, magnesium isobutylphosphonate, magnesium n-pentylphosphonate, magnesium isopentylphosphonate, magnesium n-hexylphosphonate, magnesium isoheptylphosphonate, magnesium n-heptylphosphonate, magnesium isooctylphosphonate, magnesium n-octylphosphonate, magnesium isooctylphosphonate, magnesium cyclohexylphosphonate, magnesium phenylphosphonate, magnesium benzylphosphonate, zinc phenethylphosphonate Magnesium phosphonate, titanium butylphosphonate, titanium isobutylphosphonate, titanium pentylphosphonate, titanium isopentylphosphonate, titanium hexylphosphonate, titanium isohexylphosphonate, titanium heptylphosphonate, titanium isohexylphosphonate, titanium octylphosphonate, titanium isooctylphosphonate, titanium cyclohexylphosphonate, titanium phenylphosphonate, titanium benzylphosphonate, titanium phenethylphosphonate, calcium butylphosphonate, calcium isobutylphosphonate, calcium pentylphosphonate, calcium isopentylphosphonate, calcium hexylphosphonate, calcium isohexylphosphonate, calcium heptylphosphonate At least one of the following: calcium isohepylphosphonate, calcium n-octylphosphonate, calcium isooctylphosphonate, calcium cyclohexylphosphonate, calcium phenylphosphonate, calcium benzylphosphonate, calcium phenylethylphosphonate, iron n-butylphosphonate, iron isobutylphosphonate, iron n-pentylphosphonate, iron isopentylphosphonate, iron n-hexylphosphonate, iron isohepylphosphonate, iron n-octylphosphonate, iron isooctylphosphonate, iron cyclohexylphosphonate, iron phenylphosphonate, iron benzylphosphonate, and iron phenylethylphosphonate.

[0026] An exemplary 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.

[0027] Among them, dialkyl-substituted sodium hypophosphite is at least one of the compounds of formula III. ; Among them, R 1 and R 2 Each group is independently selected from the following groups: C4~C8 straight-chain alkyl, C4~C8 branched alkyl, C4~C8 cycloalkyl, C7~C8 aralkyl, and aromatic group.

[0028] In Formula III, R 1 and R 2 They can be the same, yet they can also be different.

[0029] In Equation III, when R1 and / or R 2 When selected from C4-C8 straight-chain alkyl groups, the C4-C8 straight-chain alkyl group can be at least one of C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0030] In Equation III, when R 1 and / or R 2 When selected from C4-C8 branched alkyl groups, the C4-C8 branched alkyl groups can be at least one of C4, C5, C6, C7, or C8 branched alkyl groups. In one embodiment, the C4-C8 branched alkyl groups are at least one of (CH3)2CHCH2-, (CH3)3C-, (CH3)2CHCH2CH2-, CH3CH2CH(CH3)CH2-, (CH3)3CCH2-, (CH3)2CHCH2CH2CH2-, CH3CH(CH3)CH2CH2CH2-, (CH3)2CHCH2CH2CH2-, CH3CH2CH2CH2CH(CH3)CH2-, (CH3CH2)2CHCH2CH2-, (CH3)2CHCH2C(CH3)2CH2-, CH3CH2CH(CH2CH3)CH2CH2CH2-, or CH3CH2CH2CH2CH2CH(CH3)CH2-.

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

[0032] 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.

[0033] In Equation III, when R 1 and / or R 2 When selected from aromatic groups, the aromatic group can be phenyl.

[0034] In some embodiments, the dialkyl-substituted sodium hypophosphite used includes at least one of di-n-butyl sodium hypophosphite, diisobutyl sodium hypophosphite, bis(1,1-dimethylethyl) sodium hypophosphite, butyl(2-methylpropyl) sodium hypophosphite, di-n-pentyl sodium hypophosphite, di-n-hexyl sodium hypophosphite, di-n-heptyl sodium hypophosphite, di-n-octyl sodium hypophosphite, bis(2,4,4-trimethylpentyl) sodium hypophosphite, bis(2-ethylhexyl) sodium hypophosphite, and bis(3,3-dimethylbutyl) sodium hypophosphite.

[0035] Sodium monoalkyl phosphonate is at least one of the compounds of formula IV. ; R 3 Selected from the following groups: C4~C8 straight-chain alkyl, C4~C8 branched alkyl, C4~C8 cycloalkyl, C7~C8 aralkyl, aromatic group.

[0036] In Equation IV, when R 3 When selected from C4-C8 straight-chain alkyl groups, the C4-C8 straight-chain alkyl group can be at least one of C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0037] In Equation IV, when R 3 When selected from C4-C8 branched alkyl groups, it can be C4, C5, C6, C7, or C8 branched alkyl groups. In one embodiment, R 3 It can be (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-.

[0038] In Equation IV, when R 3 When selected from C4 to C8 cycloalkyl groups, it can be C4, C5, C6, C7, or C8 cycloalkyl.

[0039] 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 the C7-C8 aralkyl group, the alkyl moiety can be straight-chain or branched; the aromatic moiety can be phenyl.

[0040] In Equation IV, when R 3 When selected from aromatic groups, the aromatic group can be phenyl.

[0041] In some embodiments, the monoalkyl-substituted sodium hypophosphite used includes at least one of sodium n-butyl hypophosphite, sodium isobutyl hypophosphite, and sodium phenyl hypophosphite.

[0042] 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.

[0043] 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.

[0044] In one embodiment, the molar ratio of di(or mono)alkyl-substituted sodium hypophosphite to the water-soluble salt is (0.5~8):1.

[0045] 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.

[0046] 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%.

[0047] In one embodiment, the metathesis reaction is carried out under an inert atmosphere. The inert atmosphere may be nitrogen or / or argon.

[0048] 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.

[0049] Monoalkyl-substituted phosphonates can be prepared using the aforementioned methods for preparing dialkyl-substituted hypophosphonates, the only difference being that dialkyl-substituted sodium hypophosphonate is replaced with monoalkyl-substituted sodium phosphonate, wherein the monoalkyl-substituted sodium phosphonate is at least one of the compounds of formula B. , R 4 Selected from the following groups: C4~C8 straight-chain alkyl, C4~C8 branched alkyl, C4~C8 cycloalkyl, C7~C8, aromatic group.

[0050] In formula B, when R 4 When selected from C4-C8 straight-chain alkyl groups, the C4-C8 straight-chain alkyl group can be at least one of C4, C5, C6, C7 or C8 straight-chain alkyl groups.

[0051] In formula B, when R 4 When selected from C4-C8 branched alkyl groups, it can be C4, C5, C6, C7, or C8 branched alkyl groups. In one embodiment, R 3 It can be (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-.

[0052] In formula B, when R 4 When selected from C4 to C8 cycloalkyl groups, it can be C4, C5, C6, C7, or C8 cycloalkyl.

[0053] In formula B, when R 4 When selected from C7-C8 aralkyl groups, the C7-C8 aralkyl group can be at least one of C7 and C8 aralkyl groups. In the C7-C8 aralkyl group, the alkyl moiety can be straight-chain or branched; the aromatic moiety can be phenyl.

[0054] In formula B, when R 4 When selected from aromatic groups, the aromatic group can be phenyl.

[0055] In some embodiments, the monoalkyl-substituted sodium phosphonate used includes at least one of sodium n-butylphosphonate, sodium isobutylphosphonate, sodium n-pentylphosphonate, sodium isopentylphosphonate, sodium n-hexylphosphonate, sodium n-heptylphosphonate, sodium n-octylphosphonate, sodium cyclohexylphosphonate, sodium phenylphosphonate, sodium benzylphosphonate, and sodium phenethylphosphonate.

[0056] In some embodiments, when preparing monoalkyl-substituted phosphonates using sodium monoalkyl-substituted phosphonates, the reaction is carried out under an inert atmosphere. The inert atmosphere may be nitrogen or / or argon.

[0057] 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).

[0058] In some embodiments, the flame retardant composition further includes an anti-dripping agent in an amount of 0 to 3 parts by weight. In one embodiment, the anti-dripping agent is present in an amount of 0.5 to 2.5 parts by weight to improve anti-dripping performance, which is beneficial for achieving thin-walled UL-94 V-0.

[0059] 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.

[0060] In some embodiments, the flame retardant composition is prepared by mixing and dispersing the component raw materials to obtain the flame retardant composition.

[0061] Secondly, this application provides a resin composite material including the flame retardant composition.

[0062] For example, the resin 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. When the resin contains unsaturated bonds (such as ABS, HIPS, SAN, etc.), the improvement in mold fouling is more significant.

[0063] In some embodiments, the resin composite material comprises the following components in parts by weight: 65-80 parts of matrix resin and 20-35 parts of the flame retardant composition; The matrix resin includes at least one of acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and high-impact polystyrene.

[0064] By controlling the amount of resin and flame retardant composition contained in the resin composite material as described above, it not only has good flame retardancy, but also produces less mold residue during processing.

[0065] For example, the matrix resin is within the range of any two of the following: 65 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 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.

[0066] For example, the flame retardant composition is within the range 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, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, or any two of the above.

[0067] In some embodiments, the acrylonitrile-butadiene-styrene copolymer has a melt index of 6.5~75g / 10min at a temperature of 220°C and a load of 10kg, and the acrylonitrile-butadiene-styrene copolymer contains 13%~33% acrylonitrile by weight, 10%~32% butadiene by weight, and 35%~77% styrene by weight.

[0068] 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 butadiene-grafted SAN copolymer obtained by emulsion polymerization with SAN.

[0069] In some embodiments, the acrylonitrile-styrene copolymer has a melt index of 5~95g / 10min at a temperature of 220°C and a load of 10kg, and the acrylonitrile content in the acrylonitrile-styrene copolymer is 19%~34% by weight.

[0070] In some embodiments, the resin 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 2.3:7.7~3.8:6.2. The weight percentage of butadiene in the acrylonitrile-butadiene-styrene copolymer high-rubber powder can be selected as 55%~70%; the melt index of the acrylonitrile-styrene copolymer at 220℃ and a load of 10kg can be selected as 5~95g / 10min, and the weight percentage of acrylonitrile in the acrylonitrile-styrene copolymer can be selected as 19%~34%.

[0071] In some embodiments, the high-impact polystyrene has a melt index of 3~17 g / 10 min at a temperature of 200°C and a load of 5 kg, and the weight percentage of butadiene in the high-impact polystyrene is 8.3%~17.6%.

[0072] 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.

[0073] The weight percentage of monomer units in the acrylonitrile-styrene copolymer was determined by elemental analysis.

[0074] The weight percentage of monomer units in high-impact polystyrene was determined by infrared spectroscopy.

[0075] The melt index of the acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer and high-impact polystyrene was measured according to GB / T 3682-2000.

[0076] Other additives may be added to the resin 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.

[0077] 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.

[0078] 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).

[0079] 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.

[0080] 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.

[0081] 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%).

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] In some embodiments, the resin has a weight percentage of 62% or more in the resin composite material, such as 62%, 65%, 68%, 70%, 72%, 74%, 76%, 78%, 80% or more, or any two of these ranges.

[0087] In some embodiments, the flame retardant composition is present in the resin 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%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 30%, 33% or more.

[0088] In some embodiments, the preparation method of the resin composite material includes the following steps: mixing and dispersing the component raw materials, melt extrusion, granulation, and obtaining the resin composite material.

[0089] In one embodiment, melt extrusion and granulation are carried out in a twin-screw extruder when preparing the resin composite material.

[0090] 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.

[0091] Thirdly, this application provides the application of the aforementioned resin composite material in the field of electronics and electrical engineering.

[0092] Fourthly, this application provides a molded part formed from the aforementioned resin composite material. The molding method can be selected with reference to existing technologies, such as, but not limited to, injection molding, extrusion molding, blow molding, rotational molding, and / or compression molding. The resin composite material is suitable for the electronics and electrical fields and can be used to manufacture housings and components for household appliances, OA equipment (office automation equipment) housings and components, PCB (printed circuit board) protective covers, backup power supply housings, battery housings, power strip housings, etc.

[0093] Compared with the prior art, the beneficial effects of this application are as follows: By combining dialkyl-substituted phosphonates, monoalkyl-substituted phosphonates and monoalkyl-substituted phosphonates in specific amounts, and controlling the dialkyl-substituted phosphonates to contain a specific amount of dialkyl-substituted phosphonates with a tertiary carbon structure, the resulting flame retardant composition, when applied to resins, enhances the flame retardant properties of the material and reduces mold fouling during processing due to their synergistic effect, making it suitable for the preparation of electronic and electrical products. Detailed Implementation

[0094] 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.

[0095] 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 phosphinate 1: Di-n-butylphosphinate aluminum, prepared as follows: Di-n-butylphosphinate sodium is diluted with water, and the pH value is adjusted to 2.5 with sulfuric acid. Aluminum sulfate solution (aluminum sulfate content is 25wt%) 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 di-n-butylphosphinate aluminum.

[0096] Dialkyl-substituted phosphonate 2: Zinc di-n-butylphosphonate, the preparation method of which differs from that of dialkyl-substituted phosphonate 1, is that zinc chloride solution (zinc chloride content of 22wt%) is used to completely replace aluminum sulfate solution.

[0097] Dialkyl-substituted phosphinate 3: 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).

[0098] Dialkyl-substituted phosphonates 4: aluminum diethylphosphonate, whose preparation method differs from that of dialkyl-substituted phosphonates 1 in that sodium diethylphosphonate is used instead of sodium dibutylphosphonate.

[0099] Dialkyl-substituted phosphonate 5: aluminum bis(1,1-dimethylethyl)phosphonate, whose preparation method differs from that of dialkyl-substituted phosphonate 1 in that sodium bis(1,1-dimethylethyl)phosphonate is used instead of sodium dibutylphosphonate.

[0100] Dihydro-substituted phosphonate 6: Zinc bis(1,1-dimethylethyl)phosphonate, the preparation method of which differs from that of dihydro-substituted phosphonate 1 in that sodium bis(1,1-dimethylethyl)phosphonate is used instead of sodium dibutylphosphonate, and zinc chloride solution (containing 22 wt% zinc chloride) is used to completely replace aluminum sulfate solution.

[0101] Monoalkyl-substituted phosphonate 1: aluminum n-butylphosphonate, whose preparation method differs from that of dialkyl-substituted phosphonate 1 in that sodium n-butylphosphonate is used instead of sodium di-n-butylphosphonate.

[0102] Monoalkyl-substituted phosphonate 2: n-butylphosphonate zinc, the preparation method of which differs from that of monoalkyl-substituted phosphonate 1 is that zinc chloride solution (zinc chloride content is 22wt%) is used to completely replace aluminum sulfate solution.

[0103] Monoalkyl-substituted phosphinate 3: Aluminum phenylphosphinate, Hubei Chuyuebang New Material Technology Co., Ltd.

[0104] Monoalkyl-substituted phosphonates 4: Aluminum ethylphosphonate, whose preparation method differs from that of monoalkyl-substituted phosphonate 1 in that sodium ethylphosphonate is used instead of sodium n-butylphosphonate.

[0105] Monoalkyl-substituted phosphonate 1: aluminum n-butylphosphonate, whose preparation method differs from that of monoalkyl-substituted hypophosphonate 1 in that sodium n-butylphosphonate is used instead of sodium n-butylhypophosphonate.

[0106] Monoalkyl-substituted phosphonate 2: zinc n-butylphosphonate, whose preparation method differs from that of monoalkyl-substituted phosphonate 1 in that zinc chloride solution (containing 22 wt% zinc chloride) is used to completely replace aluminum sulfate solution.

[0107] Monoalkyl-substituted phosphonate 3: Aluminum ethylphosphonate, whose preparation method differs from that of monoalkyl-substituted phosphonate 11 in that sodium ethylphosphonate is used instead of sodium n-butylphosphonate.

[0108] Anti-dripping agent 1: Styrene-acrylonitrile random copolymer coated with polytetrafluoroethylene, Guangzhou Entropy Energy Innovation Materials Co., Ltd., SN80-SA7.

[0109] Anti-dripping agent 2: Styrene-methyl methacrylate copolymer coated polytetrafluoroethylene, Shanghai Puxin Polymer Materials Co., Ltd., DB109.

[0110] ABS Resin 1: Emulsion method, Ningbo LG Yongxing Chemical Co., Ltd., HI-121H.

[0111] ABS Resin 2: Bulk method, DOW, grade ABS 8434.

[0112] 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.

[0113] HIPS resin: Guoheng Chemical Co., Ltd., PS 350K.

[0114] SAN resin: Liaoning Kingfa Science & Technology Co., Ltd., KFA-130.

[0115] PBT resin: China Changchun Group, PBT 1200-211M.

[0116] PA resin: PA6, Haiyang Technology Co., Ltd., PA6 HY-2500A.

[0117] Polyolefin: Polypropylene, CNOOC Shell Petrochemicals Co., Ltd., PP HP500N.

[0118] 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.

[0119] The formulations of flame retardant compositions 1 to 8 are shown in Tables 1 and 2. Their preparation methods include the following steps: mixing and dispersing the raw materials of each component to obtain the flame retardant composition.

[0120] Table 1 Table 2 Examples 1-3 and Comparative Examples 1-2 These examples and comparative examples all provide a resin composite material, and their preparation methods include the following steps: According to the formulation of the resin composite material in Table 3, the raw materials of each component are mixed and dispersed, fed into a twin-screw extruder for melt extrusion and granulation to obtain the resin composite material. The twin-screw extruder has twin screw temperatures of 60℃, 120℃, 180℃, 200℃, 200℃, 200℃, 200℃, 200℃, 220℃, screw speed of 350 rpm, screw length-to-diameter ratio of 40:1, and feeding speed of 35 kg / h.

[0121] Table 3 The resin composite materials of the above embodiments and comparative examples were subjected to the following performance tests: (1) Flame retardancy: The resin composite material was injection molded into a standard sample with a thickness of 3.0 mm. The vertical burning flame retardancy performance of the sample was tested according to the UL94-2023 standard, and the average value of t1+t2 was determined. (2) Mold fouling: A KraussMaffei injection molding machine is used to inject square plates, with an venting groove at the end of the plate. During injection, a small metal sheet is placed in the venting groove. After multiple injections, the decomposition gases are cooled through the venting groove and gradually deposited on the metal sheet. Injection process: Material temperature 240℃, 200 molds are continuously injected, and the deposit of mold fouling on the metal sheet is visually observed. Severity of mold fouling: Less mold fouling, the lower surface can be clearly seen through the mold fouling collection point; moderate mold fouling, the lower surface can be vaguely seen through the mold fouling collection point; severe mold fouling, the lower surface of the mold cannot be seen through the mold fouling collection point.

[0122] The test results are shown in Table 4, where “NG” indicates that the V-2 level was not achieved.

[0123] Table 4 As can be seen from the above data, the resin composite materials of the above embodiments not only have good flame retardancy, but also produce less mold fouling during processing. For example, the flame retardancy (thickness 3.0mm) reaches V-0 level, the average value of t1+t2 is below 9.5 s, and the mold fouling level is less or average.

[0124] In Comparative Example 1, the dihydro-substituted phosphonate does not have a tertiary carbon structure, resulting in a deviation in flame retardancy.

[0125] In Comparative Example 2, the flame retardancy of the materials was poor and the mold fouling was severe because the number of carbon atoms in the hydrocarbon groups of the dihydrophosphinates, monohydrophosphinates, and monohydrophosphinates that do not have tertiary carbon structures was low.

[0126] Examples 4-8 These embodiments all provide a resin composite material, and their preparation methods differ from those of Embodiment 1 in that the formulations are different, as detailed in Table 5.

[0127] Table 5 Flame retardancy and mold fouling performance tests were conducted on Examples 4-8. The test method here differed from the previous test methods in that, for the flame retardancy performance test, the resin composite material was injection molded into a standard specimen with a thickness of 1.5 mm. The test results are shown in Table 6.

[0128] Table 6 As shown in Table 6, by adding an appropriate amount of anti-dripping agent to the flame retardant composition, UL-94 V-0 / 1.5mm can be achieved. Moreover, the resin composite material is less prone to mold fouling during processing, making it suitable for preparing thinner-walled products.

[0129] Examples 9-11 These embodiments all provide a resin composite material, and their preparation methods differ from those of Embodiment 1 in that the formulations are different, as detailed in Table 7.

[0130] Table 7 Flame retardancy tests were conducted on Examples 9-11. The test method here differed from the previous test methods in that the resin composite material was injection molded into a standard specimen with a thickness of 1.5 mm for the flame retardancy performance test. The test results are shown in Table 8.

[0131] Table 8 As shown in Table 8, the resin composite materials of Examples 9-11 have good flame retardancy and can achieve UL-94 V-0 / 1.5mm.

[0132] 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: 75-95 parts of dialkyl-substituted phosphonates, 4.7-20 parts of monoalkyl-substituted phosphonates, and 0.1-5 parts of monoalkyl-substituted phosphonates; The dialkyl-substituted phosphonate is at least one of the compounds of formula I, the monoalkyl-substituted phosphonate is at least one of the compounds of formula II, and the monoalkyl-substituted phosphonate is at least one of the compounds of formula A. ， Among them, R 1 R 2 R 3 and R 4 Each group is independently selected from the following groups: C4-C8 straight-chain alkyl, C4-C8 branched alkyl, C4-C8 cycloalkyl, C7-C8 aralkyl, and aromatic group; X, Y, and Z are each independently selected from Al, Mg, Ca, Zn, Ti, or Fe; n, m, and a are each independently selected from integers between 2 and 4; The dialkyl-substituted phosphonate comprises a dialkyl-substituted phosphonate having a tertiary carbon structure; the dialkyl-substituted phosphonate having a tertiary carbon structure is 0.08 to 7 parts by weight.

2. The flame retardant composition according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The dialkyl-substituted phosphines with tertiary carbon structures include aluminum bis(1,1-dimethylethyl)phosphines, aluminum bis(2-methylpropyl)phosphines, aluminum butyl(2-methylpropyl)phosphines, aluminum bis(2,4,4-trimethylpentyl)phosphines, aluminum bis(2-ethylhexyl)phosphines, aluminum bis(3,3-dimethylbutyl)phosphines, zinc bis(1,1-dimethylethyl)phosphines, zinc bis(2-methylpropyl)phosphines, and aluminum butyl(2-methylpropyl)phosphines. Zinc bis(2-methylpropyl)phosphine, zinc bis(2,4,4-trimethylpentyl)phosphine, zinc bis(2-ethylhexyl)phosphine, zinc bis(3,3-dimethylbutyl)phosphine, magnesium bis(1,1-dimethylethyl)phosphine, magnesium bis(2-methylpropyl)phosphine, magnesium butyl(2-methylpropyl)phosphine, magnesium bis(2,4,4-trimethylpentyl)phosphine, magnesium bis(2-ethylhexyl)phosphine, magnesium bis(3,3-dimethyl)phosphine Butyl(2-methylpropyl) phosphine magnesium, bis(1,1-dimethylethyl) phosphine titanium, bis(2-methylpropyl) phosphine titanium, butyl(2-methylpropyl) phosphine titanium, bis(2,4,4-trimethylpentyl) phosphine titanium, bis(2-ethylhexyl) phosphine titanium, bis(3,3-dimethylbutyl) phosphine titanium, bis(1,1-dimethylethyl) phosphine calcium, bis(2-methylpropyl) phosphine calcium, butyl(2-methylpropyl) phosphine calcium, At least one of the following: bis(2,4,4-trimethylpentyl)phosphonic acid calcium, bis(2-ethylhexyl)phosphonic acid calcium, bis(3,3-dimethylbutyl)phosphonic acid calcium, bis(1,1-dimethylethyl)phosphonic acid iron, bis(2-methylpropyl)phosphonic acid iron, butyl(2-methylpropyl)phosphonic acid iron, bis(2,4,4-trimethylpentyl)phosphonic acid iron, bis(2-ethylhexyl)phosphonic acid iron, and bis(3,3-dimethylbutyl)phosphonic acid iron; (2) The dialkyl-substituted phosphinates include 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 di-n-butylphosphinate, zinc diisobutylphosphinate, zinc di-n-pentylphosphinate, zinc diisopentylphosphinate, zinc di-n-hexylphosphinate, zinc di-n-heptylphosphinate, zinc di-octylphosphinate, zinc diphenylethylphosphinate, magnesium di-n-butylphosphinate, magnesium diisobutylphosphinate, magnesium di-n-pentylphosphinate, magnesium diisopentylphosphinate, magnesium di-n-hexylphosphinate, magnesium di-n-heptylphosphinate, magnesium di-octylphosphinate, and zinc diphenylethylphosphinate. Magnesium phosphinate, di-n-butyl phosphinate titanium, diisobutyl phosphinate titanium, di-n-pentyl phosphinate titanium, diisopentyl phosphinate titanium, di-n-hexyl phosphinate titanium, di-n-heptyl phosphinate titanium, di-n-octyl phosphinate titanium, diphenylethyl phosphinate titanium, di-n-butyl phosphinate calcium, diisobutyl phosphinate calcium, di-n-pentyl phosphinate calcium, diisopentyl phosphinate calcium, di-n-hexyl phosphinate calcium, di-n-heptyl phosphinate calcium, di-n-octyl phosphinate calcium, di-n-butyl phosphinate iron, diisobutyl phosphinate iron, di-n-pentyl phosphinate iron, diisopentyl phosphinate iron, di-n-hexyl phosphinate iron, di-n-heptyl phosphinate iron, di-n-octyl phosphinate iron, diphenylethyl phosphinate iron; (3) The monoalkyl-substituted phosphinates include 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 n-butylphosphinate, zinc isobutylphosphinate, zinc n-pentylphosphinate, and zinc isopentylphosphinate. Zinc hexyl phosphinate, zinc heptyl phosphinate, zinc octyl phosphinate, zinc cyclohexyl phosphinate, zinc phenyl phosphinate, zinc benzyl phosphinate, zinc phenethyl 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 phosphinate, n-butyl titanium phosphinate, isobutyl titanium phosphinate, n-pentyl titanium phosphinate, isopentyl titanium phosphinate, n-hexyl titanium phosphinate, n-heptyl titanium phosphinate, n-octyl titanium phosphinate, cyclohexyl titanium phosphinate, phenyl titanium phosphinate, benzyl titanium phosphinate, phenethyl titanium phosphinate, n-butyl calcium phosphinate, isobutyl calcium phosphinate, n-pentyl calcium phosphinate, isopentyl calcium phosphinate, n-hexyl calcium phosphinate, n-heptyl At least one of the following: calcium phosphite, octyl calcium phosphite, cyclohexyl calcium phosphite, phenyl calcium phosphite, benzyl calcium phosphite, phenylethyl calcium phosphite, ferric butyl phosphite, ferric isobutyl phosphite, ferric pentyl phosphite, ferric isopentyl phosphite, ferric phenyl phosphite, ferric methyl phosphite, ferric hexyl phosphite, ferric octyl phosphite, ferric cyclohexyl phosphite, ferric phenyl phosphite, ferric benzyl phosphite, and ferric phenylethyl phosphite; (4) The monoalkyl-substituted phosphonates include aluminum n-butylphosphonate, aluminum isobutylphosphonate, aluminum n-pentylphosphonate, aluminum isopentylphosphonate, aluminum n-hexylphosphonate, aluminum isohexylphosphonate, aluminum n-heptylphosphonate, aluminum isoheptylphosphonate, aluminum n-octylphosphonate, aluminum isooctylphosphonate, aluminum cyclohexylphosphonate, aluminum phenylphosphonate, aluminum benzylphosphonate, aluminum phenethylphosphonate, zinc n-butylphosphonate, zinc isobutylphosphonate, zinc n-pentylphosphonate, zinc isopentylphosphonate, zinc n-hexylphosphonate, and zinc isohexylphosphonate. Zinc phosphonate, zinc n-heptylphosphonate, zinc isoheptylphosphonate, zinc n-octylphosphonate, zinc isooctylphosphonate, zinc cyclohexylphosphonate, zinc phenylphosphonate, zinc benzylphosphonate, zinc phenethylphosphonate, magnesium n-butylphosphonate, magnesium isobutylphosphonate, magnesium n-pentylphosphonate, magnesium isopentylphosphonate, magnesium n-hexylphosphonate, magnesium isoheptylphosphonate, magnesium n-octylphosphonate, magnesium isooctylphosphonate, magnesium cyclohexylphosphonate, magnesium phenylphosphonate, magnesium benzylphosphonate, zinc phenethylphosphonate Magnesium phosphonate, titanium butylphosphonate, titanium isobutylphosphonate, titanium pentylphosphonate, titanium isopentylphosphonate, titanium hexylphosphonate, titanium isohexylphosphonate, titanium heptylphosphonate, titanium isohexylphosphonate, titanium octylphosphonate, titanium isooctylphosphonate, titanium cyclohexylphosphonate, titanium phenylphosphonate, titanium benzylphosphonate, titanium phenethylphosphonate, calcium butylphosphonate, calcium isobutylphosphonate, calcium pentylphosphonate, calcium isopentylphosphonate, calcium hexylphosphonate, calcium isohexylphosphonate, calcium heptylphosphonate At least one of the following: calcium isohepylphosphonate, calcium n-octylphosphonate, calcium isooctylphosphonate, calcium cyclohexylphosphonate, calcium phenylphosphonate, calcium benzylphosphonate, calcium phenylethylphosphonate, iron n-butylphosphonate, iron isobutylphosphonate, iron n-pentylphosphonate, iron isopentylphosphonate, iron n-hexylphosphonate, iron isohepylphosphonate, iron n-octylphosphonate, iron isooctylphosphonate, iron cyclohexylphosphonate, iron phenylphosphonate, iron benzylphosphonate, and iron phenylethylphosphonate.

3. 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 0.5 to 2.5 parts by weight.

4. The flame retardant composition according to claim 3, 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.

5. A resin composite material, characterized in that, Includes the flame retardant composition as described in any one of claims 1 to 4.

6. The resin composite material as described in claim 5, characterized in that, The resin in the resin composite material includes at least one of acrylonitrile-butadiene-styrene copolymer, high-impact polystyrene, polyamide, polybutylene terephthalate, acrylonitrile-styrene copolymer, and polyolefin.

7. The resin composite material as described in claim 5, characterized in that, It comprises the following components in parts by weight: 65-80 parts of matrix resin, and 20-35 parts of the flame retardant composition; The matrix resin includes at least one of acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and high-impact polystyrene.

8. The resin composite material as described in claim 7, characterized in that, At least one of the following conditions must be met: (5) The melt index of the acrylonitrile-butadiene-styrene copolymer at a temperature of 220°C and a load of 10kg is 6.5~75g / 10min, and in the acrylonitrile-butadiene-styrene copolymer, the weight percentage of acrylonitrile is 13%~33%, the weight percentage of butadiene is 10%~32%, and the weight percentage of styrene is 35%~77%; (6) The melt index of the acrylonitrile-styrene copolymer at a temperature of 220°C and a load of 10kg is 5~95g / 10min, and the weight percentage of acrylonitrile in the acrylonitrile-styrene copolymer is 19~34%; (7) The matrix resin includes acrylonitrile-butadiene-styrene copolymer high-rubber powder and acrylonitrile-styrene copolymer, wherein the weight ratio of the acrylonitrile-butadiene-styrene copolymer high-rubber powder to the acrylonitrile-styrene copolymer is 2.3:7.7~3.8:6.2; (8) The melt index of the high-impact polystyrene under the conditions of 200℃ and 5kg load is 3~17g / 10min, and the weight ratio of butadiene in the high-impact polystyrene is 8.3%~17.6%.

9. The application of the resin composite material as described in any one of claims 5 to 8 in the field of electronics and electrical engineering.

10. A molded part, characterized in that, It is formed from the resin composite material as described in any one of claims 5 to 8.

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