Halogen-free swelling flame-retardant system containing benzoxazine charcoal forming agent and flame-retardant thermoplastic resin of halogen-free swelling flame-retardant system

Abstract

The invention relates to a halogen-free swelling flame-retardant system containing a benzoxazine charcoal forming agent and flame-retardant thermoplastic resin of the halogen-free swelling flame-retardant system. The halogen-free swelling flame-retardant system is prepared from the following raw materials in percentage by weight: 40%-95% of a phosphorus-nitrogen flame retardant, 2%-50% of the benzoxazine charcoal forming agent, 0-30% of a nitrogen-containing compound and 0-15% of a synergist, wherein the benzoxazine charcoal forming agent is one or more of single-oxazine-ring benzoxazine, bisphenol benzoxazine or diamine double-oxazine-ring benzoxazine. By virtue of the benzoxazine charcoal forming agent in the flame-retardant system, the dispersion of the added flame-retardant system in apolymer base material is promoted, the separation and migration of small-molecular flame-retardant components are inhibited, more stable charcoal layers can be generated in the combustion process, and the thermal insulation and the oxygen insulation are realized, so that the flame-retardant system has relatively high flame-retardant efficiency. Besides, a proper amount of silane structures are introduced into benzoxazine molecules, so that the flame-retardant system has the phosphorus-nitrogen-silicon ternary synergetic flame-retardant effect and can play a role of a silane coupling agent, and the comprehensive performance of a composite material is further improved.

Description

technical field

[0001] The invention belongs to the field of polymer materials, and relates to a halogen-free expansion flame-retardant system containing a benzoxazine char-forming agent and a flame-retardant thermoplastic resin thereof. Background technique

[0002] Thermoplastic resins account for about 90% of the world's total synthetic resins, commonly used are polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate ( PMMA), polyoxymethylene (POM), polyamide (PA), polyphenylene oxide (PPO), polyester, etc. Thermoplastic resins can be softened by repeated heating and solidified by cooling. They have good characteristics of being recyclable, reusable, and non-polluting to the environment. They are in line with the current development direction of green and environment-friendly materials. They are easy to process and mold, and have a wide range of applications. However, most thermoplastic resins have poor heat resistance, ...

Examples

Embodiment 1

[0042] The weight ratio of 69.9% POM, 20% ammonium polyphosphate, 6% melamine, 3% bisphenol A aniline benzoxazine and 1% phenolic benzoxazine, 0.1% nanometer montmorillonite and a small amount of antioxidant 1010 Premix on a high-speed mixer for 10 minutes, then melt, extrude and granulate in a twin-screw extruder at 165-175°C, and inject into molding on an injection molding machine.

[0043] Wherein the preparation method structural formula of bisphenol A aniline type benzoxazine used is identical with comparative example 1, and the preparation method of phenol type benzoxazine is similar to the preparation method of bisphenol A aniline type benzoxazine in comparative example 1, It is synthesized from 4-cyanophenol, 3-aminopropyltriethoxysilane and paraformaldehyde at a molar ratio of 1:1:2, and its structural formula is as follows:

[0044]

[0045] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 41.5%, and the vertic...

Embodiment 2

[0047] The weight ratio of 69.7% POM, 20% ammonium polyphosphate, 6% melamine, 2% bisphenol A aniline benzoxazine and 2% bisphenol F aniline benzoxazine, 0.3% graphene oxide and a small amount of antioxidant Agent 1010 was pre-mixed on a high-speed mixer for 10 minutes, then melted and extruded in a twin-screw extruder at 165-175°C to granulate, and then injection-molded on an injection molding machine.

[0048] Wherein the structural formula of bisphenol A aniline benzoxazine used is the same as that of comparative example 1, and the preparation method of bisphenol F aniline benzoxazine is similar to that of bisphenol A aniline benzoxazine in comparative example 1 , synthesized by bisphenol F, aniline and paraformaldehyde in a molar ratio of 1:2:4, its structural formula is as follows:

[0049]

[0050] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 49.7%, and the vertical burning is V-1 level.

Embodiment 3

[0052] Premix 72% POM, 20% ammonium polyphosphate, 6% melamine, 2% silane-containing bisphenol A type benzoxazine and a small amount of antioxidant 1010 on a high-speed mixer for 10 minutes, and then extrude on a twin-screw Melt and extrude at 165-175°C to granulate in the exiting machine, and then injection-molded on the injection molding machine.

[0053] The preparation method of bisphenol A type benzoxazine containing silane structure used is similar to the preparation method of bisphenol A aniline type benzoxazine in Comparative Example 1, by bisphenol A, 3-aminopropyltriethoxysilane and Paraformaldehyde is synthesized at a molar ratio of 1:2:4, and its structural formula is as follows:

[0054]

[0055] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 52.1%, and the vertical burning is V-0 level.

technical field

[0001] The invention belongs to the field of polymer materials, and relates to a halogen-free expansion flame-retardant system containing a benzoxazine char-forming agent and a flame-retardant thermoplastic resin thereof. Background technique

[0002] Thermoplastic resins account for about 90% of the world's total synthetic resins, commonly used are polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate ( PMMA), polyoxymethylene (POM), polyamide (PA), polyphenylene oxide (PPO), polyester, etc. Thermoplastic resins can be softened by repeated heating and solidified by cooling. They have good characteristics of being recyclable, reusable, and non-polluting to the environment. They are in line with the current development direction of green and environment-friendly materials. They are easy to process and mold, and have a wide range of applications. However, most thermoplastic resins have poor heat resistance, ...

Examples

Embodiment 1

[0042] The weight ratio of 69.9% POM, 20% ammonium polyphosphate, 6% melamine, 3% bisphenol A aniline benzoxazine and 1% phenolic benzoxazine, 0.1% nanometer montmorillonite and a small amount of antioxidant 1010 Premix on a high-speed mixer for 10 minutes, then melt, extrude and granulate in a twin-screw extruder at 165-175°C, and inject into molding on an injection molding machine.

[0043] Wherein the preparation method structural formula of bisphenol A aniline type benzoxazine used is identical with comparative example 1, and the preparation method of phenol type benzoxazine is similar to the preparation method of bisphenol A aniline type benzoxazine in comparative example 1, It is synthesized from 4-cyanophenol, 3-aminopropyltriethoxysilane and paraformaldehyde at a molar ratio of 1:1:2, and its structural formula is as follows:

[0044]

[0045] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 41.5%, and the vertic...

Embodiment 2

[0047] The weight ratio of 69.7% POM, 20% ammonium polyphosphate, 6% melamine, 2% bisphenol A aniline benzoxazine and 2% bisphenol F aniline benzoxazine, 0.3% graphene oxide and a small amount of antioxidant Agent 1010 was pre-mixed on a high-speed mixer for 10 minutes, then melted and extruded in a twin-screw extruder at 165-175°C to granulate, and then injection-molded on an injection molding machine.

[0048] Wherein the structural formula of bisphenol A aniline benzoxazine used is the same as that of comparative example 1, and the preparation method of bisphenol F aniline benzoxazine is similar to that of bisphenol A aniline benzoxazine in comparative example 1 , synthesized by bisphenol F, aniline and paraformaldehyde in a molar ratio of 1:2:4, its structural formula is as follows:

[0049]

[0050] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 49.7%, and the vertical burning is V-1 level.

Embodiment 3

[0052] Premix 72% POM, 20% ammonium polyphosphate, 6% melamine, 2% silane-containing bisphenol A type benzoxazine and a small amount of antioxidant 1010 on a high-speed mixer for 10 minutes, and then extrude on a twin-screw Melt and extrude at 165-175°C to granulate in the exiting machine, and then injection-molded on the injection molding machine.

[0053] The preparation method of bisphenol A type benzoxazine containing silane structure used is similar to the preparation method of bisphenol A aniline type benzoxazine in Comparative Example 1, by bisphenol A, 3-aminopropyltriethoxysilane and Paraformaldehyde is synthesized at a molar ratio of 1:2:4, and its structural formula is as follows:

[0054]

[0055] The limiting oxygen index of the obtained halogen-free intumescent flame-retardant polyoxymethylene is 52.1%, and the vertical burning is V-0 level.

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