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CN-118006123-B - Low-acidity halogen-free flame retardant, preparation method thereof, flame-retardant polyamide composite material and application

CN118006123BCN 118006123 BCN118006123 BCN 118006123BCN-118006123-B

Abstract

The invention discloses a low-acidity halogen-free flame retardant which comprises 89-96 parts by weight of dialkyl aluminum hypophosphite and 5-10 parts by weight of hindered amine light stabilizer, wherein the pH value of the low-acidity halogen-free flame retardant is 6.5-7. The invention can improve the corrosiveness of the flame retardant to the resin matrix, improve the flame retardant property and the oxygen isolation property and reduce the corrosiveness to rubber when being applied to the polyamide composition by reducing the acidity of the halogen-free flame retardant and containing the specific content of the hindered amine light stabilizer.

Inventors

  • LU XIANBO
  • LIN JIELONG
  • YE SHIBING
  • ZHANG YONG
  • LIU JIQING
  • AN PENG

Assignees

  • 上海金发科技发展有限公司
  • 金发科技股份有限公司
  • 江苏金发科技新材料有限公司

Dates

Publication Date
20260508
Application Date
20240315

Claims (10)

  1. 1. The low-acidity halogen-free flame retardant is characterized by comprising the following components in parts by weight: 89-96 parts of dialkyl aluminum hypophosphite, 5-10 Parts of hindered amine light stabilizer, The pH value of the low-acidity halogen-free flame retardant is 6.5-7; The preparation method of the low-acidity halogen-free flame retardant comprises the following steps of weighing 1-5 parts of calcium oxide, 40-98 parts of water, 1-5 parts of aluminum ammonium sulfate, 90-95 parts of dialkyl aluminum hypophosphite and 5-10 parts of hindered amine light stabilizer, dissolving the calcium oxide and the aluminum ammonium sulfate in the water, adjusting the pH value to 6.5-7 by using 5-15wt% of dilute hydrochloric acid, adding the dialkyl aluminum hypophosphite and the hindered amine light stabilizer, stirring for 0.5-3 hours, controlling the temperature to 60-90 ℃ during the stirring, standing for 5-15 hours, filtering, and drying to obtain the low-acidity halogen-free flame retardant.
  2. 2. The low-acidity halogen-free flame retardant according to claim 1, wherein the method for testing the pH value of the low-acidity halogen-free flame retardant is characterized in that 500 mg low-acidity halogen-free flame retardant is taken, 50 ml deionized water is added, the mixture is placed in an 80 ℃ ultrasonic water bath kettle and is fully stirred for 15min, the mixed solution is added into a centrifuge tube for high-speed centrifugation operation, and then the pH value of supernatant is tested.
  3. 3. The low acidity halogen-free flame retardant of claim 1 wherein the aluminum dialkylphosphinate is selected from the group consisting of aluminum diethylphosphinate.
  4. 4. The low-acidity halogen-free flame retardant of claim 1, wherein the hindered amine light stabilizer is at least one selected from the group consisting of a high molecular hindered amine light stabilizer and a low molecular hindered amine light stabilizer; the macromolecular hindered amine light stabilizer is selected from 1,5,8, 12-tetra [4, 6-bis (N-butyl-N-1, 2, 6-pentamethyl-4-piperidylamino) -1,3, 5-triazin-2-yl ] -1,5,8, 12-tetraazadodecane Poly- { [6- [ (1, 3-tetramethylbutyl) -imino ] -1,3, 5-triazin-2, 4-diyl ] [2- (2, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2, 6-tetramethylpiperidinyl) -imino ], poly [1- (2 '-hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidinedioic acid ester ], tetra (1, 2, 6-pentamethyl-4-piperidinyl) 1,2,3, 4-butanetetracarboxylate, N, polymers of N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and 2,4, 6-trichloro-1, 3, 5-triazine and N-butyl-1-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine, at least one of poly { (6-morpholino-5-triazine-2, 4-diyl) (2, 6-tetramethylpiperidinyl) iminohexamethylene [ (2, 6-tetramethylpiperidinyl) -imino ] }; the low molecular hindered amine light stabilizer is selected from bis-2, 6-tetramethyl piperidinol sebacate and N, N '-diformyl-N, N' -bis (2, 6-tetramethyl-4-piperidine) -hexamethylenediamine, 1,2,3, 4-butanetetracarboxylic acid tetrakis (1, 2, 6-pentamethyl-4-piperidinyl) ester at least one of 2, 6-tetramethyl-4-piperidinyl stearate.
  5. 5. The low acidity halogen-free flame retardant of claim 4 wherein the hindered amine light stabilizer is selected from the group consisting of polymeric hindered amine light stabilizers.
  6. 6. The low acidity halogen-free flame retardant of claim 5, characterized in that, the macromolecular hindered amine light stabilizer is selected from poly- { [6- [ (1, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2, 6-tetramethylpiperidinyl) -imino ]: at least one of poly [1- (2' -hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidine succinate ].
  7. 7. A flame-retardant polyamide composite material is characterized by comprising, by weight, 30-80 parts of polyamide resin and 20-40 parts of the low-acidity halogen-free flame retardant according to any one of claims 1-6.
  8. 8. The flame retardant polyamide composite according to claim 7, wherein said polyamide resin is at least one selected from the group consisting of aliphatic polyamide resins, semiaromatic polyamide resins and polylactam resins.
  9. 9. The flame retardant polyamide composite material according to claim 7, further comprising 0 to 1 part by weight of a heat stabilizer selected from the group consisting of phenolic heat stabilizers and thiosulfate antioxidants.
  10. 10. Use of a flame retardant polyamide composite material according to any of claims 7-9 for the preparation of rubber-contacting electronic and electrical parts, rubber-contacting vehicle fittings.

Description

Low-acidity halogen-free flame retardant, preparation method thereof, flame-retardant polyamide composite material and application Technical Field The invention relates to the technical field of high polymer materials, in particular to a low-acidity halogen-free flame retardant, a preparation method thereof, a flame-retardant polyamide composite material and application thereof. Background The hypophosphite flame retardant has higher phosphorus content, can be used as a flame retardant or a flame retardant synergist, but has the defect that the hypophosphite flame retardant has strong acidity and can cause degradation, equipment corrosion and migration precipitation of high polymer materials, and the problems limit the use of the hypophosphite flame retardant as the flame retardant. Particularly, the polyamide resin is obviously influenced by acid components, so that the acid of the material is reduced on the premise of not influencing the flame retardant property of the material, thereby effectively reducing the corrosiveness of the material and having important economic value. Meanwhile, the applicant finds through experiments that the addition of the commercial dialkyl aluminum hypophosphite flame retardant can obviously reduce the oxygen barrier property of the polyamide composite material, accelerate the internal oxidation process of the material, shorten the service life and reduce the application of the polyamide composite material in the fields of electronic appliances, electric tools and automobiles. Meanwhile, the commercial dialkyl aluminum hypophosphite flame retardant can also make the polyamide composite material corrosive to contacted rubber materials, and influence the application of the polyamide composite material in new energy automobile parts (such as connectors, connectors and the like). The prior art does not report on the improvement method of the related defects. Disclosure of Invention The invention aims to overcome the technical defects and provide a low-acidity halogen-free flame retardant with low acidity, good flame retardance and improved oxygen barrier property of a polyamide composition, and a preparation method and application thereof. The invention is realized by the following technical scheme: The low-acidity halogen-free flame retardant comprises the following components in parts by weight: 89-96 parts of dialkyl aluminum hypophosphite, 5-10 Parts of hindered amine light stabilizer, The pH value of the low-acidity halogen-free flame retardant is 6.5-7. The method for testing the pH value of the low-acidity halogen-free flame retardant comprises the steps of adding 500 mg low-acidity halogen-free flame retardant into 50 ml deionized water, placing the mixture in an 80 ℃ ultrasonic water bath kettle, fully stirring for 15min, adding the mixed solution into a centrifuge tube for high-speed centrifugation operation, and then testing the pH value of supernatant. The dialkylaluminum hypophosphite is selected from diethylaluminum hypophosphite. The hindered amine light stabilizer is at least one selected from a high molecular hindered amine light stabilizer and a low molecular hindered amine light stabilizer, and the high molecular hindered amine light stabilizer is at least one selected from the following substances: 1,5,8, 12-tetrakis [4, 6-bis (N-butyl-N-1, 2, 6-pentamethyl-4-piperidylamino) -1,3, 5-triazin-2-yl ] -1,5,8, 12-tetraazadodecane (CAS: 106990-43-6), Poly- { [6- [ (1, 3-tetramethylbutyl) -imino ] -1,3, 5-triazin-2, 4-diyl ] [2- (2, 6) -tetramethylpiperidinyl) -amino ] -hexylene- [4- (2, 6-tetramethylpiperidinyl) -imino ] (CAS: 70624-18-9), Poly [1- (2' -hydroxyethyl) -2, 6-tetramethyl-4-hydroxypiperidine succinate ] (CAS: 65447-77-0), Tetra (1, 2, 6-pentamethyl-4-piperidinyl) 1,2,3, 4-butanetetracarboxylate (CAS: 91788-83-9) (LA-52), Polymers of N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexanediamine and 2,4, 6-trichloro-1, 3, 5-triazine and N-butyl-1-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine (CAS: 192268-64-7), Poly { (6-morpholino-5-triazine-2, 4-diyl) (2, 6-tetramethylpiperidinyl) iminohexamethylene [ (2, 6-tetramethylpiperidinyl) -imino ] } (CAS: 82451-48-7). The low molecular hindered amine light stabilizer is at least one selected from the following substances: bis-2, 6-tetramethylpiperidinol sebacate (CAS: 52829-07-9), N, N '-diformyl-N, N' -bis (2, 6-tetramethyl-4-piperidine) -hexamethylenediamine (CAS: 124172-53-8), Tetra (1, 2, 6-pentamethyl-4-piperidinyl) 1,2,3, 4-butanetetracarboxylate (CAS: 91788-83-9), 2, 6-Tetramethyl-4-piperidinyl stearate (CAS: 167078-06-0). Preferably, the hindered amine light stabilizer is selected from polymeric hindered amine light stabilizers; it is further preferred that the composition of the present invention, the high molecular hindered amine light stabilizer is selected from poly- { [6- [ (1, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2, 6-tetramethylpiperidinyl) -amino ] -hexyl-