Halogen-free flame retardant and polymer material containing same

Abstract

The invention discloses a halogen-free flame retardant and a polymer material containing the same. The halogen-free flame retardant contains a compound A and a compound B, wherein the compound A is selected from at least one of non-acid metal salts formed by an acid radical anion and a metal cation, wherein the acid radical anion is formed by at least one hydroxyl in a compound C by losing of a hydrogen atom; the compound C is selected from at least one of the compounds having the chemical formula shown in formula (I); the compound B is selected from at least one of the compounds having the chemical formula shown in formula (II) and the compounds having the chemical formula shown in formula (III). The halogen-free flame retardant overcomes defects of existing alkyl phosphonates as flame retardants, and particularly solves the problems of polymer material degradation and yellowing caused by the alkyl phosphonates in the prior art.

Description

technical field

[0001] The application relates to a halogen-free flame retardant and a polymer material containing the flame retardant, belonging to the field of preparation of flame retardant polymer materials. Background technique

[0002] Flame-retardant polymer materials, especially glass fiber reinforced polyamide, polyester PBT and high-temperature nylon, are widely used in the manufacture of electrical sockets, connectors, relays and other small electronic components in the electronics and electrical industry. Traditionally, the flame retardancy of polymer materials is realized by brominated flame retardants, but brominated flame retardants can produce strong carcinogenic dioxins when burned, and the hydrogen bromide produced at the same time can cause secondary pollution. Therefore, the use of brominated flame retardants has been gradually restricted in recent years, and the flame retardancy of polymer materials has thus turned to halogen-free flame retardants. [0...

Examples

Embodiment 1

[0101] Preparation of ATMP-Zn

[0102] Add 50wt% ATMP aqueous solution (173.00g, 0.29 moles) in a 500mL beaker, add dropwise 25wt% NaOH aqueous solution at room temperature, adjust pH to 6~7, consume altogether 231.32 grams (1.45 moles of NaOH) of NaOH aqueous solution, equivalent to To neutralize 5 acids in ATMP, leaving 1 acid. At room temperature, under stirring at a stirring speed of 300 to 400 rpm, it was added dropwise to 1000mL containing 30wt% ZnSO 4 ·7H 2 O (207.50g, 0.72mol) aqueous solution was added dropwise in a beaker within 1.5h, and stirred at room temperature for 0.5h. Suction filtration, water washing and drying were then carried out successively to obtain a white powdery solid, 120.84 g in total, with a yield of 91.50%, which was recorded as ATMP-Zn.

Embodiment 2

[0104] Preparation of ATMP-Zn-Ca Mixed Salt

[0105] Add 50wt% ATMP aqueous solution (19.38g, 0.0324 mol) in a 200mL beaker, add dropwise 10wt% NaOH aqueous solution at room temperature, adjust pH to 7, consume 66.4 grams (0.166 mol) NaOH aqueous solution altogether, be equivalent to neutralizing 5.12 acids in ATMP. At room temperature, under stirring at a stirring speed of 300 to 400 rpm, add it dropwise until CaCl is dissolved. 2 (1.86g, 0.0168 mol) and ZnCl 2 (9.09g, 0.0668 mole) (wherein Zn / Ca molar ratio = 4 / 1), the dropwise addition was completed within 40min, and stirred at room temperature for 0.5h. Suction filtration, water washing and drying were then carried out successively to obtain a white powdery solid, 13.17 g in total, with a yield of 90.1%, which was recorded as ATMP-Zn-Ca.

Embodiment 3

[0107] Mix polyamide PA66-B, DePAl-1, ATMP-Zn and compound antioxidant according to the weight ratio of 79.6:15:5:0.4 in an internal mixer with a rotating speed of 50 rpm and set the temperature at 280 ℃, after 5 minutes, take it out to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 280°C for 10 minutes, hold the pressure at 10MPa for 5 minutes, and then cold press it. The sample is off-white, and after it cools down, cut the sample and test it. The flame retardancy grades of the 1.6mm sample and the 0.8mm are both V-0.

technical field

[0001] The application relates to a halogen-free flame retardant and a polymer material containing the flame retardant, belonging to the field of preparation of flame retardant polymer materials. Background technique

[0002] Flame-retardant polymer materials, especially glass fiber reinforced polyamide, polyester PBT and high-temperature nylon, are widely used in the manufacture of electrical sockets, connectors, relays and other small electronic components in the electronics and electrical industry. Traditionally, the flame retardancy of polymer materials is realized by brominated flame retardants, but brominated flame retardants can produce strong carcinogenic dioxins when burned, and the hydrogen bromide produced at the same time can cause secondary pollution. Therefore, the use of brominated flame retardants has been gradually restricted in recent years, and the flame retardancy of polymer materials has thus turned to halogen-free flame retardants. [0...

Examples

Embodiment 1

[0101] Preparation of ATMP-Zn

[0102] Add 50wt% ATMP aqueous solution (173.00g, 0.29 moles) in a 500mL beaker, add dropwise 25wt% NaOH aqueous solution at room temperature, adjust pH to 6~7, consume altogether 231.32 grams (1.45 moles of NaOH) of NaOH aqueous solution, equivalent to To neutralize 5 acids in ATMP, leaving 1 acid. At room temperature, under stirring at a stirring speed of 300 to 400 rpm, it was added dropwise to 1000mL containing 30wt% ZnSO 4 ·7H 2 O (207.50g, 0.72mol) aqueous solution was added dropwise in a beaker within 1.5h, and stirred at room temperature for 0.5h. Suction filtration, water washing and drying were then carried out successively to obtain a white powdery solid, 120.84 g in total, with a yield of 91.50%, which was recorded as ATMP-Zn.

Embodiment 2

[0104] Preparation of ATMP-Zn-Ca Mixed Salt

[0105] Add 50wt% ATMP aqueous solution (19.38g, 0.0324 mol) in a 200mL beaker, add dropwise 10wt% NaOH aqueous solution at room temperature, adjust pH to 7, consume 66.4 grams (0.166 mol) NaOH aqueous solution altogether, be equivalent to neutralizing 5.12 acids in ATMP. At room temperature, under stirring at a stirring speed of 300 to 400 rpm, add it dropwise until CaCl is dissolved. 2 (1.86g, 0.0168 mol) and ZnCl 2 (9.09g, 0.0668 mole) (wherein Zn / Ca molar ratio = 4 / 1), the dropwise addition was completed within 40min, and stirred at room temperature for 0.5h. Suction filtration, water washing and drying were then carried out successively to obtain a white powdery solid, 13.17 g in total, with a yield of 90.1%, which was recorded as ATMP-Zn-Ca.

Embodiment 3

[0107] Mix polyamide PA66-B, DePAl-1, ATMP-Zn and compound antioxidant according to the weight ratio of 79.6:15:5:0.4 in an internal mixer with a rotating speed of 50 rpm and set the temperature at 280 ℃, after 5 minutes, take it out to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 280°C for 10 minutes, hold the pressure at 10MPa for 5 minutes, and then cold press it. The sample is off-white, and after it cools down, cut the sample and test it. The flame retardancy grades of the 1.6mm sample and the 0.8mm are both V-0.

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