Phosphorus carbonic ester flame retardant, ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof

Abstract

The invention provides a phosphorus-based carbonate flame retardant, an ABS composite material and a preparation method thereof, the phosphorus-based carbonate flame retardant has a structure as shown in a formula I, has excellent flame retardant property and can promote rapid carbon formation of ABS resin, the phosphorus-based carbonate flame retardant is compounded with a synergistic flame retardant, and the flame retardant efficiency is improved. According to the present invention, the obtained ABS composite material can have the optimal flame retardant effect, has excellent mechanical properties, and particularly has high notch impact strength.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a phosphorus-based carbonate flame retardant, an ABS composite material and a preparation method thereof. Background Art

[0002] ABS resin is a thermoplastic polymer widely used in industry and daily life. It is copolymerized from three monomers: acrylonitrile (A), butadiene (B) and styrene (S), and has good mechanical properties, processing properties and cost-effectiveness. ABS resin is widely used in the manufacture of household appliance shells, electronic devices, automotive parts and other products due to its toughness, rigidity and heat resistance. However, ABS resin is flammable, which limits its use in specific application fields that require high flame retardant standards.

[0003] To improve the flame retardant performance of ABS resin, flame retardants are usually added. Traditional flame retardants, such as halogen-containing flame retardants, especially organic halogen flame retardants, although they can effectively improve the flame retardant performance of ABS resin, may release toxic gases during combustion, posing a threat to the environment and human health, and may also affect the mechanical properties and processing properties of ABS resin; in addition, existing environmentally friendly halogen-free phosphorus-based flame retardants applied to ABS, such as phosphate ester flame retardants, although environmentally friendly, usually require a high addition amount and cannot reach the ideal flame retardant grade. In addition, the high addition amount may seriously affect the mechanical properties of ABS resin, resulting in a decline in the mechanical properties of ABS resin.

[0004] Therefore, in view of the above technical problems, there is an urgent need to develop a phosphorus-based carbonate flame retardant that is environmentally friendly, has excellent flame retardant performance and does not affect the mechanical properties of ABS resin itself. Summary of the Invention

[0005] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a phosphorus-based carbonate flame retardant, an ABS composite material and a preparation method and application thereof. The phosphorus-based carbonate flame retardant has an efficient flame retardant effect, can effectively improve the flame retardant performance of ABS resin with a low addition amount, and when compounded with a synergistic flame retardant, can effectively improve the flame retardant performance of the obtained ABS composite material, while not affecting the excellent mechanical properties and processing properties of ABS resin itself, and is very environmentally friendly.

[0006] To achieve the purpose of the present invention, the following technical solutions are adopted:

[0007] The present invention provides a phosphorus-based carbonate flame retardant, and the phosphorus-based carbonate flame retardant has a structure shown in the following formula I:

[0008]

[0009] The phosphorus-based carbonate flame retardant provided by the present invention has the structure shown in the above formula I, and it mainly relies on the combination of condensed-phase flame retardancy and gas-phase flame retardancy. The carbonate groups contained in the structure can decompose to produce a large amount of non-combustible gas carbon dioxide at high temperatures, which can effectively reduce the activity of combustible gas molecules, and thus has excellent flame retardancy. Moreover, it can promote the rapid carbonization of ABS resin at high temperatures to form a flame-retardant mixture, thereby achieving efficient flame retardancy for ABS resin.

[0010] In a second aspect, the present invention provides a preparation method of the phosphorus-based carbonate flame retardant as described in the first aspect. The preparation method includes the following steps:

[0011] (1) React allylmagnesium bromide with diphenylphosphine chloride to obtain allyldiphenylphosphine;

[0012] (2) React the allyldiphenylphosphine obtained in step (1) with hydrogen peroxide to obtain allyldiphenylphosphine oxide;

[0013] (3) React the allyldiphenylphosphine oxide obtained in step (2) with m-chloroperoxybenzoic acid to obtain (3-glycidyloxypropyl)diphenylphosphine oxide;

[0014] (4) React the (3-glycidyloxypropyl)diphenylphosphine oxide obtained in step (3) with carbon dioxide to obtain the phosphorus-based carbonate flame retardant.

[0015] Preferably, the temperature of the reaction in step (1) is 20 - 40°C, such as 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, 32°C, 34°C, 36°C, 38°C or 40°C, etc., and more preferably 25 - 35°C.

[0016] Preferably, the time of the reaction in step (1) is 0.5 - 1.5 h, such as 0.5 h, 0.7 h, 0.9 h, 1.1 h, 1.3 h or 1.5 h, etc.

[0017] Preferably, the molar ratio of allylmagnesium bromide to diphenylphosphine chloride in step (1) is 1:(1.1 - 1.3), such as 1:1.1, 1:1.15, 1:1.2, 1:1.25 or 1:1.3, etc.

[0018] Preferably, the temperature of the reaction in step (2) is 20 - 40°C, such as 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, 32°C, 34°C, 36°C, 38°C or 40°C, etc., and more preferably 25 - 35°C.

[0019] Preferably, the time of the reaction in step (2) is 0.5 - 1.5 h, such as 0.5 h, 0.7 h, 0.9 h, 1.1 h, 1.3 h or 1.5 h, etc.

[0020] Preferably, the molar ratio of allyldiphenylphosphine to hydrogen peroxide in step (2) is 1:(9-11), such as 1:9, 1:9.5, 1:10, 1:10.5, or 1:11, etc.

[0021] In the present invention, the hydrogen peroxide can be added in the form of hydrogen peroxide solution, and the present invention has no special requirements for the concentration of the hydrogen peroxide solution. It is possible to select common hydrogen peroxide solutions with a concentration of 3-90 wt%, for example, 30 wt% hydrogen peroxide solution can be directly selected.

[0022] Preferably, the temperature of the reaction in step (3) is 20-40 °C, such as 20 °C, 22 °C, 24 °C, 26 °C, 28 °C, 30 °C, 32 °C, 34 °C, 36 °C, 38 °C, or 40 °C, etc.

[0023] Preferably, the reaction time in step (3) is 5-7 h, such as 5 h, 5.2 h, 5.4 h, 5.6 h, 5.8 h, 6 h, 6.2 h, 6.4 h, 6.6 h, 6.8 h, or 7 h, etc.

[0024] Preferably, the molar ratio of allyldiphenylphosphine oxide to m-chloroperbenzoic acid in step (3) is 1:(1-1.3), such as 1:1, 1:1.1, 1:1.15, 1:1.2, 1:1.25, or 1:1.3, etc.

[0025] Preferably, the temperature of the reaction in step (4) is 30-50 °C, such as 32 °C, 34 °C, 36 °C, 38 °C, 40 °C, 42 °C, 44 °C, 46 °C, 48 °C, or 50 °C, etc.

[0026] Preferably, the reaction time in step (4) is 3-5 days, such as 3 days, 3.2 days, 3.4 days, 3.6 days, 3.8 days, 4 days, 4.2 days, 4.4 days, 4.6 days, 4.8 days, or 5 days, etc.

[0027] Preferably, the reaction pressure in step (4) is 200-450 kPa, such as 200 kPa, 220 kPa, 240 kPa, 260 kPa, 280 kPa, 400 kPa, 440 kPa, or 450 kPa, etc.

[0028] Preferably, the molar ratio of (3-glycidyloxypropyl)diphenylphosphine oxide to carbon dioxide in step (4) is 1:(2-7), such as 1:2, 1:3, 1:5, 1:5.2, 1:5.4, 1:5.6, 1:5.8, 1:6, 1:6.2, 1:6.4, 1:6.6, 1:6.8, or 1:7, etc.

[0029] As a preferred technical solution of the present invention, the method includes the following steps:

[0030] (1) Synthesis of allyldiphenylphosphine: Allylmagnesium bromide and diphenylphosphine chloride were reacted in a tetrahydrofuran solvent. After quenching the reaction with water, extraction was carried out with dichloromethane. After drying, suction filtration, and solvent evaporation under reduced pressure, a yellow viscous crude product was obtained. After purification by column chromatography, allyldiphenylphosphine was obtained.

[0031] The reaction formula for step (1) is:

[0032] (2) Synthesis of allyldiphenylphosphine oxide: The allyldiphenylphosphine obtained in step (1) was dissolved in dichloromethane, and hydrogen peroxide was added thereto for reaction. After the reaction was completed, the organic phase was washed successively with an anhydrous sodium sulfite solution and a saturated brine until the starch KI test paper showed no blue change. After drying, suction filtration, and solvent evaporation under reduced pressure, a transparent oily crude product was obtained. Finally, after purification by column chromatography, allyldiphenylphosphine oxide was obtained.

[0033] The reaction formula for step (2) is:

[0034] (3) Synthesis of (3 - glycidyloxypropyl)diphenylphosphine oxide: The allyldiphenylphosphine oxide obtained in step (2) was dissolved in dichloromethane, anhydrous sodium bicarbonate was added, and then meta - chloroperoxybenzoic acid (mCPBA) was added for reaction. After the reaction was completed, the mixture was washed successively with a sodium sulfite solution, a sodium bicarbonate solution, and a saturated brine. After drying, suction filtration, and solvent evaporation under reduced pressure, a transparent viscous crude product was obtained. Finally, after purification by column chromatography, (3 - glycidyloxypropyl)diphenylphosphine oxide was obtained.

[0035] The reaction formula for step (3) is:

[0036] (4) Synthesis of the phosphorus - based carbonate flame retardant having the structure shown in Formula I: The (3 - glycidyloxypropyl)diphenylphosphine oxide obtained in step (3) and tetrabutylammonium bromide were added to a reaction kettle. After purging the air with high - purity CO₂, CO₂ was charged for reaction. After the reaction was completed, CO₂ was released and the pressure was reduced. The product was dissolved in ethyl acetate, washed with deionized water and saturated brine, and then after drying, suction filtration, and solvent evaporation under reduced pressure, finally, after purification by column chromatography, a pale yellow solid was obtained, which is the phosphorus - based carbonate flame retardant having the structure shown in Formula I.

[0037] The reaction formula for step (4) is:

[0038] Thirdly, the present invention provides an ABS composite material, and the ABS composite material comprises the following components by weight:

[0039] 80 - 90 parts by weight of ABS resin;

[0040] 15 to 25 parts by weight of the phosphorus-based carbonate flame retardant as described in the first aspect;

[0041] 1 to 5 parts by weight of the synergistic flame retardant.

[0042] The ABS composite material provided by the present invention uses the phosphorus-based carbonate flame retardant and the synergistic flame retardant as described in the first aspect of the present invention for compounding, thereby realizing efficient flame retardancy of the ABS resin, being very environmentally friendly, halogen-free, and not affecting the excellent mechanical properties and processing properties of the ABS resin itself, enabling the obtained ABS resin to have both excellent flame retardant properties and mechanical properties, especially a relatively high notched impact strength.

[0043] In the present invention, the dosage of the ABS resin can be 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 or 90 parts by weight, and in the ABS composite material, the mass percentage content of the ABS resin is not less than 75%.

[0044] In the present invention, the dosage of the phosphorus-based carbonate flame retardant can be 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight or 25 parts by weight, etc.

[0045] In the present invention, the dosage of the synergistic flame retardant can be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.

[0046] Preferably, the melt index of the ABS resin under the test conditions of 220 °C and 10 kg is 40 to 45 g / 10 min, such as 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min or 45 g / 10 min, etc.

[0047] In the present invention, the melt index of the above ABS resin can be tested by referring to the method provided in "ASTM D1238-2010".

[0048] Preferably, the content of the phosphorus-based carbonate flame retardant in the ABS composite material is 18 to 22 parts by weight, such as 18 parts by weight, 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight, 20 parts by weight, 20.5 parts by weight, 21 parts by weight, 21.5 parts by weight or 22 parts by weight, etc.

[0049] Preferably, the synergistic flame retardant includes antimony trioxide.

[0050] Preferably, the mass ratio of the phosphorus-based carbonate flame retardant to the synergistic flame retardant is (3-11):1, such as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1 or 11:1, etc.

[0051] Preferably, other additives are further included in the ABS composite material.

[0052] Preferably, the content of other additives in the ABS composite material is 0.5-2 parts by weight, such as 0.5 part by weight, 0.7 part by weight, 0.9 part by weight, 1.1 part by weight, 1.3 part by weight, 1.5 part by weight, 1.7 part by weight, 1.9 part by weight or 2 parts by weight, etc.

[0053] Preferably, the other additives include an antioxidant and / or a lubricant.

[0054] In the present invention, there are no special requirements for the selection of the types of the antioxidant and the lubricant. Conventional antioxidants and lubricants in the art can be selected. Exemplarily: the antioxidant can be selected from antioxidant 1010, antioxidant 168, etc.; the lubricant can be selected from vinyl bisstearamide (EBS), etc.

[0055] Fourthly, the present invention provides a preparation method of the ABS composite material as described in the third aspect. The preparation method includes: mixing an ABS resin, the phosphorus-based carbonate flame retardant as described in the first aspect, a synergist and optionally other additives, and performing melt extrusion granulation to obtain the ABS composite material.

[0056] Preferably, the mixing time is 3-5 min, such as 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min or 5 min, etc.

[0057] Preferably, the melt extrusion granulation is carried out in a twin-screw extruder.

[0058] The numerical ranges described in the present invention not only include the point values exemplified above, but also include any point values between the above numerical ranges not exemplified. Due to space limitations and for the sake of brevity, the specific point values included in the ranges of the present invention are not exhaustively listed.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] (1) The phosphorus-based carbonate flame retardant with the structure shown in Formula I provided by the present invention has excellent flame retardant properties. The carbonate group contained therein can decompose to generate a large amount of non-combustible gas carbon dioxide at high temperature, thereby effectively reducing the activity of combustible gas molecules. At the same time, it can promote the rapid carbonization of ABS resin at high temperature to form a flame-retardant mixture, thereby achieving efficient flame retardancy for ABS resin;

[0061] (2) The ABS composite material provided by the present invention includes an ABS resin, a phosphorus-based carbonate flame retardant with the structure shown in Formula I, and a synergistic flame retardant. By compounding the phosphorus-based carbonate flame retardant with the structure shown in Formula I and the synergistic flame retardant, the obtained ABS composite material has the best flame retardant effect, can achieve a flame retardancy of V-0 level in UL-94 for flame retardancy, and has excellent mechanical properties, especially a relatively high notched impact strength. Description of the Drawings

[0062] Figure 1 1H-NMR spectrum of allyldiphenylphosphine oxide obtained in step (2) of Example 1; 1 1H-NMR spectrum;

[0063] Figure 2 13C-NMR spectrum of allyldiphenylphosphine oxide obtained in step (2) of Example 1; 13 13C-NMR spectrum;

[0064] Figure 3 31P-NMR spectrum of allyldiphenylphosphine oxide obtained in step (2) of Example 1; 31 31P-NMR spectrum;

[0065] Figure 4 1H-NMR spectrum of (3-glycidyl)diphenylphosphine oxide obtained in step (3) of Example 1; 1 1H-NMR spectrum;

[0066] Figure 5 13C-NMR spectrum of (3-glycidyl)diphenylphosphine oxide obtained in step (3) of Example 1; 13 13C-NMR spectrum;

[0067] Figure 6 31P-NMR spectrum of (3-glycidyl)diphenylphosphine oxide obtained in step (3) of Example 1; 31 31P-NMR spectrum;

[0068] Figure 7 1H-NMR spectrum of the phosphorus-based carbonate flame retardant provided in Example 1; 1 1H-NMR spectrum;

[0069] Figure 8 13C-NMR spectrum of the phosphorus-based carbonate flame retardant provided in Example 1; 13 13C-NMR spectrum. Detailed Description of the Invention

[0070] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0071] Unless otherwise specified, the materials involved in the following specific embodiments are all conventional materials in the art and can be obtained through commercial purchase;

[0072] In particular, the information of some raw materials involved is as follows:

[0073] (1) ABS resin: The melt index under the test conditions of 220 °C and 10 kg is 24 g / 10 min, purchased from Liaoning Jinfa;

[0074] (2) Synergistic flame retardant: Antimony trioxide, purchased from Hunan Flash Star;

[0075] (3) Phosphorus-based flame retardant: PX-220, commercially available.

[0076] Example 1

[0077] Example 1 provides a phosphorus-based carbonate flame retardant having a structure shown in the following formula I:

[0078]

[0079] The reaction formula of the phosphorus-based carbonate flame retardant provided in this example is as follows:

[0080]

[0081] The preparation method of the phosphorus-based carbonate flame retardant provided in this example includes the following steps:

[0082] (1) Synthesis of allyldiphenylphosphine: Under nitrogen protection, 10 mol of allylmagnesium bromide was injected into a sealed reaction device containing 25 mL of tetrahydrofuran to prepare a Grignard reagent; subsequently, 13 mol of diphenylphosphine chloride was dissolved in 15 mL of purified tetrahydrofuran and slowly added dropwise to the Grignard reagent at liquid nitrogen temperature through a constant pressure dropping funnel; after the addition was completed, the reaction was stirred at room temperature for 1 h. After the reaction ended, the reaction was quenched with deionized water and extracted with dichloromethane. After drying and suction filtration, the solvent was evaporated under reduced pressure to obtain a yellow viscous crude product; finally, it was purified by column chromatography to obtain a pale yellow viscous target product;

[0083] (2) Synthesis of allyldiphenylphosphine oxide: Add 10 mol of allyldiphenylphosphine obtained in step (1) into a round-bottom flask and dissolve it with 25 mL of dichloromethane. While stirring, add dropwise 30 wt% H2O2 (containing a total of 100 mol of hydrogen peroxide). After the addition is complete, stir and react at 30 °C for 1 h. After the reaction is completed, wash the organic phase successively with sodium sulfite solution and saturated brine until the starch KI test paper shows no blue change. After drying, suction filtration, and solvent evaporation under reduced pressure, a transparent oily crude product is obtained. Finally, it is purified by column chromatography to obtain the target product as a white powder.

[0084] (3) Synthesis of (3-glycidyloxypropyl)diphenylphosphine oxide: Place 10 mol of allyldiphenylphosphine oxide obtained in step (2) in a round-bottom flask and dissolve it with 25 mL of dichloromethane. While stirring, add 3 g of anhydrous sodium bicarbonate, and then slowly add 10 mol of m-chloroperbenzoic acid (mCPBA). React at 30 °C for 6 h. After the reaction is completed, wash successively with sodium sulfite solution, sodium bicarbonate solution, and saturated brine. After drying, perform suction filtration, and obtain a transparent viscous crude product by solvent evaporation under reduced pressure. Finally, it is purified by column chromatography to obtain the target product as white granules.

[0085] (4) Synthesis of phosphorus-based carbonate flame retardant: Add 10 mol of (3-glycidyloxypropyl)diphenylphosphine oxide obtained in step (4), 1.5 g of tetrabutylammonium bromide, and a magnetic stirrer into an autoclave and seal it. Flush the air three times with high-purity CO2, charge 25 mol of CO2, and pressurize to make the pressure in the autoclave 303 kPa. Stir and react at 40 °C for 4 days. After completion, release CO2 to reduce the pressure, dissolve the product with 30 mL of ethyl acetate, wash with deionized water and saturated brine, perform suction filtration after drying, and evaporate the solvent under reduced pressure. Finally, it is purified by column chromatography to obtain a pale yellow solid, which is the phosphorus-based carbonate flame retardant having the structure shown in Formula I.

[0086] Structure characterization:

[0087] Use a nuclear magnetic resonance spectrometer (Bruker, NMR - 500 Hz) to test allyldiphenylphosphine oxide obtained in step (2), (3-glycidyloxypropyl)diphenylphosphine oxide obtained in step (3), and the phosphorus-based carbonate flame retardant having the structure shown in Formula I obtained in step (4) respectively.

[0088] ① The 1 1H-NMR spectrum, 13 13C-NMR spectrum, and 31 31P-NMR spectrum of allyldiphenylphosphine oxide obtained in step (2) are respectively as shown in Figures 1 to 3 , and the results are as follows:

[0089] 11H NMR (500 MHz, Chloroform-d) δ 3.14 (dd, J = 14.54, 7.38 Hz, 2H), 5.07–5.22 (m, 2H), 5.80 (dp, J = 16.18, 8.60, 7.97 Hz, 1H), 7.42–7.55 (m, 6H), 7.69–7.78 (m, 4H).

[0090] 13 13C NMR (126 MHz, Chloroform-d) δ 35.12 (d, J = 68.89 Hz), 119.98 (d, J = 11.74 Hz), 126.00 (d, J = 9.12 Hz), 127.56 (d, J = 11.71 Hz), 130.00 (d, J = 9.19 Hz), 130.81 (d, J = 2.73 Hz), 130.98 – 131.14 (s), 131.84 (s);

[0091] 31 31P NMR (202 MHz, Chloroform-d) δ 29.75;

[0092] In summary, allyldiphenylphosphine oxide was successfully synthesized in step (2) of Example 1.

[0093] ② The 1H-NMR spectrum, 1 13C-NMR spectrum and 13 31P-NMR spectrum of (3-glycidyloxy)diphenylphosphine oxide obtained in step (3) were tested and are shown respectively as 31 follows, and the results are as follows: Figures 4 to 6 shown below:

[0094] 1 1H NMR (500 MHz, Chloroform-d) δ 2.31 (td, J = 14.39, 6.74 Hz, 1H), 2.48 (dd, J = 4.65, 2.53 Hz, 1H), 2.72 (t, J = 4.28 Hz, 1H), 2.80 (ddd, J = 15.44, 10.62, 5.24 Hz, 1H), 3.22 (tq, J = 6.65, 3.70 Hz, 1H), 7.42–7.56 (m, 6H), 7.74 (ddd, J = 20.87, 10.08, 4.14 Hz, 4H);

[0095] 1313C NMR (126 MHz, Chloroform-d) δ 33.00 (s), 33.54 (s), 43.61–48.75 (m), 127.74 (dd, J=11.90, 3.07 Hz), 129.77 (dd, J=22.55, 9.69 Hz), 130.80 (s), 131.10 (dd, J =6.37, 2.76 Hz), 131.25 (s), 131.59 (s), 132.05 (s);

[0096] 31 31P NMR (202 MHz, Chloroform-d) δ 30.25;

[0097] In summary, in step (3), (3-glycidyl)diphenylphosphine oxide was successfully synthesized.

[0098] ③ Obtaining the phosphorus-based carbonate flame retardant with the structure shown in Formula I 1 1H-NMR spectrum and 13 13C-NMR spectrum are respectively as Figures 7 to 8 shown, and the results are as follows:

[0099] 1 1H NMR (500 MHz, Chloroform-d) δ 2.67 (td, J=13.96, 10.40 Hz, 1H), 2.94 (ddd, J=13.90, 9.75, 3.77 Hz, 1H), 4.33 (dd, J=9.07, 7.43 Hz, 1H), 4.48–4.56 (m, 1H), 4.90 (dq, J=11.13, 7.52, 5.60 Hz, 1H), 7.40–7.55 (m, 6H), 7.68 (ddd, J=23.56, 11.96, 7.22 Hz, 4H);

[0100] 13 13C NMR (126 MHz, Chloroform-d) δ 33.63 (s), 34.16 (s), 69.12 (s), 71.57 (s), 128.10 (dd, J=12.13, 8.69 Hz), 129.34 (d, J=9.85 Hz), 129.73 (d, J=9.72 Hz), 131.62 (t, J=2.98 Hz), 153.18 (s).

[0101] In summary, in Example 1, the phosphorus-based carbonate flame retardant with the structure shown in Formula I was successfully synthesized.

[0102] Application Examples 1-7 and Comparative Application Examples 1-3

[0103] Application Examples 1-7 and Comparative Application Examples 1-3 respectively provide an ABS composite material, and the components and dosages thereof are shown in Table 1. In Table 1, the dosage unit of each component is "parts by weight".

[0104] Table 1

[0105]

[0106]

[0107] The preparation methods of the ABS composite materials provided by Application Examples 1-7 and Comparative Application Examples 1-3 include the following steps:

[0108] Dry-mix the pre-dried components according to the composition formula in Table 1 in a mixer at about 100 revolutions per minute for 4 minutes, and then melt-extrude and pelletize the mixed raw materials in a twin-screw extruder with a length-diameter ratio of 40:1, a temperature range of 160 °C, 190 °C, 190 °C, 200 °C, 210 °C, 210 °C, 210 °C, 220 °C, 220 °C, 220 °C, 220 °C, and a rotational speed of 450 revolutions per minute to obtain the ABS composite material.

[0109] Performance testing:

[0110] (1) Flame retardancy rating: Test according to the UL94 standard, and the thickness of the test sample is 2-3 mm.

[0111] (2) Notched impact strength: Test according to the method provided by the test standard GB / T1843-1996.

[0112] Test the ABS composite materials provided by Application Examples 1-7 and Comparative Application Examples 1-5 according to the above test methods, and the test results are shown in Table 2:

[0113] Table 2

[0114]

[0115]

[0116] It can be seen from the data in Table 2 that:

[0117] The ABS composite materials provided by Application Examples 1-7 have both excellent flame retardancy and impact resistance. Specifically, the flame retardancy level is V-1 to V-0, and the notched impact strength is 16-25 kJ m -2 , especially the flame retardancy levels of the ABS composite materials provided by Application Examples 1-3 can reach V-0, and the notched impact strength is as high as 22-25 kJ m -2 , having the most excellent flame retardancy and impact resistance.

[0118] Comparing the data of Application Example 1 and Comparative Application Examples 1-2, it can be found that if the addition amount of the phosphorus-based carbonate flame retardant is too low, the flame retardant grade of the obtained ABS composite material will not reach V-2, and the flame retardant performance is very poor; while if the addition amount of the phosphorus-based carbonate flame retardant is too high, the impact resistance of the obtained ABS composite material will be very poor, and the notch impact strength is only 12 kJ m -2 , and it is impossible to have both excellent flame retardant performance and impact resistance.

[0119] Comparing the data of Application Example 1 and Comparative Application Example 3, it can also be seen that using the conventional phosphorus-based flame retardant PX-220 will result in the flame retardant grade of the obtained ABS composite material being only V-2, and the flame retardant performance is very poor.

[0120] Finally, comparing the data of Application Example 1 and Application Examples 4-7, it can also be seen that the addition amount of the phosphorus-based carbonate flame retardant and the addition ratio of the phosphorus-based carbonate flame retardant to the synergistic flame retardant will also affect the flame retardant performance and impact resistance of the finally obtained ABS composite material. The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A phosphorus-based carbonate flame retardant, characterized in that, The phosphorus-based carbonate flame retardant has a structure shown in the following formula I:

2. A preparation method of the phosphorus-based carbonate flame retardant as described in claim 1, characterized in that, The preparation method includes the following steps: (1) React allylmagnesium bromide with diphenylphosphine chloride to obtain allyldiphenylphosphine; (2) React the allyldiphenylphosphine obtained in step (1) with hydrogen peroxide to obtain allyldiphenylphosphine oxide; (3) React the allyldiphenylphosphine oxide obtained in step (2) with m-chloroperoxybenzoic acid to obtain (3-glycidyl)diphenylphosphine oxide; (4) React the (3-glycidyl)diphenylphosphine oxide obtained in step (3) with carbon dioxide to obtain the phosphorus-based carbonate flame retardant.

3. An ABS composite material, characterized in that, The ABS composite material comprises the following components by weight: 80-90 parts by weight of ABS resin; 15-25 parts by weight of the phosphorus-based carbonate flame retardant as described in claim 1; 1-5 parts by weight of a synergistic flame retardant.

4. The ABS composite material according to claim 3, wherein The melt index of the ABS resin under the test conditions of 220 °C and 10 kg is 10-45 g / 10 min.

5. The ABS composite material according to claim 3 or 4, characterized in that The content of the phosphorus-based carbonate flame retardant in the ABS composite material is 18-22 parts by weight.

6. The ABS composite material according to any one of claims 3 to 5, characterized in that The synergistic flame retardant includes antimony trioxide; Preferably, the mass ratio of the phosphorus-based carbonate flame retardant to the synergistic flame retardant is (3-11):1, and more preferably (5-10):

1.

7. The ABS composite material according to any one of claims 3 to 6, characterized in that The ABS composite material further includes other additives; Preferably, the content of other additives in the ABS composite material is 0.5-2 parts by weight; Preferably, the other additives include an antioxidant and / or a lubricant.

8. A method for preparing an ABS composite material according to any one of claims 3 to 7, characterized in that, The preparation method includes: mixing the ABS resin, the phosphorus-based carbonate flame retardant as described in claim 1, the synergistic flame retardant and optionally other additives, and performing melt extrusion granulation to obtain the ABS composite material.

9. The preparation method according to claim 8, wherein, The mixing time is 3-5 min.

10. The preparation method according to claim 8 or 9, characterized in that, The melt extrusion granulation is carried out in a twin-screw extruder.

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