CN108276749B - A halogen-free flame retardant and resin alloy containing the halogen-free flame retardant - Google Patents

Abstract

The invention discloses a halogen-free flame retardant and a resin alloy containing the same, wherein the halogen-free flame retardant consists of the following components: 1-10 parts of carbon nano tube nano particles, 10-20 parts of carboxylated carbon nano tube nano particles, 5-10 parts of metal oxide mixture, 20-40 parts of expandable graphite nano particles and 15-30 parts of phosphorus-containing halogen-free compound. The halogen-free flame retardant of the invention improves the flame retardant grade of resin and simultaneously does not reduce or greatly reduce the mechanical property of resin alloy.

Description

A halogen-free flame retardant and resin alloy containing the halogen-free flame retardant

technical field

The invention relates to the field of resin alloys, in particular to a halogen-free flame retardant and a resin alloy containing the halogen-free flame retardant.

Background technique

When a fire occurs, halogen-containing flame retardant materials will generate a large amount of smoke and toxic corrosive hydrogen halide gas during the flame retardant process, causing secondary hazards. The new flame retardant system produces less smoke when burning and does not produce toxic and corrosive gases. Halogen-free flame retardant additives are mainly based on phosphorus-based compounds and metal hydroxides. These two types of compounds do not volatilize and produce no corrosive gas during combustion, and are called pollution-free flame retardants. In addition, there are several new types of halogen-free flame retardants such as silicon-based flame retardants and nitrogen-based flame retardants. These new halogen-free flame retardants have become new products in line with the development trend of international standards. However, in order to improve the flame retardant level of the resin, more flame retardants are usually added to the resin composition to meet the requirements for the flame retardant level. However, as the amount of flame retardant added increases, the mechanical properties of the resin composition will Affected, but the addition amount is too small to meet the requirements of flame retardant grade.

SUMMARY OF THE INVENTION

In view of this, the purpose of the present invention is to provide a halogen-free flame retardant and a resin alloy containing the halogen-free flame retardant, the halogen-free flame retardant does not reduce or greatly reduce the flame retardant grade of the resin while improving the flame retardant grade of the resin. Mechanical properties of resin alloys.

In order to solve the above-mentioned technical problems, the technical solution adopted in the present invention is as follows: a halogen-free flame retardant, which is composed of the following components: 1-10 parts by weight of carbon nanotube nanoparticles, 10-20 parts by weight of carboxylated carbon nanotube nano-particles particles, 5-10 parts by weight of the metal oxide mixture, 20-40 parts by weight of expandable graphite nanoparticles, and 15-30 parts by weight of a phosphorus-containing halogen-free compound.

In the above halogen-free flame retardant, the carbon nanotube nanoparticles are one or both of single-layer carbon nanotube nanoparticles and multi-layer carbon nanotube nanoparticles.

In the above halogen-free flame retardant, the carbon nanotube nanoparticles are composed of 1-6 parts by weight of single-walled carbon nanotube nanoparticles and 3-5 parts by weight of multi-layer carbon nanotube nanoparticles.

In the above halogen-free flame retardant, the carboxylated carbon nanotube nanoparticles are one or both of carboxylated single-walled carbon nanotube nanoparticles and carboxylated multi-layered carbon nanotube nanoparticles.

In the above halogen-free flame retardant, the carboxylated carbon nanotube nanoparticles are composed of 2-7 parts by weight of carboxylated single-walled carbon nanotube nanoparticles and 3-6 parts by weight of carboxylated multi-layered carbon nanotube nanoparticles.

In the above halogen-free flame retardant, the mole fraction of carboxyl groups of the carboxylated single-walled carbon nanotube nanoparticles is 50-80%, and the mole fraction of carboxylation of the carboxylated multi-layer carbon nanotube nanoparticles is 50-60%.

In the above halogen-free flame retardant, the metal oxide mixture is a mixture of titanium dioxide nanoparticles, magnesium oxide nanoparticles and aluminum oxide nanoparticles.

In the above halogen-free flame retardant, the phosphorus-containing halogen-free compound is composed of polyphosphate, tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane) Any one of alkane-4-methylene) phosphate and 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane or two or more.

In the above halogen-free flame retardant, the phosphorus-containing halogen-free compound is composed of 10-15 parts by weight of polyphosphate ester, 1-6 parts by weight of tris(1-oxo-1-phospha-2,6,7-trioxo) Heterobicyclo[2,2,2]octane-4-methylene)phosphate and 2-8 parts by weight of 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phospha Bicyclo[2,2,2]octane composition.

The resin alloy containing the above halogen-free flame retardant is composed of the following components: 40-60 parts by weight of polycarbonate resin, 20-30 parts by weight of acrylonitrile-butadiene-styrene copolymer, 6-30 parts by weight of non- Halogen flame retardant, 6-12 parts by weight of compatibilizer and 2-4 parts by weight of processing aid; the compatibilizer consists of the following components: 30-50 parts by weight of diene oligomer, 8-20 parts by weight Maleic anhydride and 3-17 parts by weight of acrylic acid; the diene oligomer is composed of 1-4 parts by weight of butadiene oligomer with a relative molecular mass of 600-2000 g/mol, 2-4 parts by weight of a butadiene oligomer with an average molecular weight of 600-2000 g/mol It is composed of pentadiene oligomers with a relative molecular mass of 1200-3000g/mol and 3-5 parts by weight of hexadiene oligomers with a weight-average molecular mass of 2400-3600g/mol; the processing aids include antioxidants agent, lubricant and mold release agent, the antioxidant is composed of 1.6 parts by weight of citric acid, 0.8 parts by weight of tocopherol, 1.6 parts by weight of ascorbic acid and 2.0 parts by weight of phosphite; the lubricant is 1.6 parts by weight of stearic acid A mixture of lanthanum, 1.2 parts by weight of zinc stearate, 1.6 parts by weight of polyethylene wax and 0.8 parts by weight of pentaerythritol stearate; the release agent is a mixture of 0.8 parts by weight of silicone oil release agent and 1.6 parts by weight of microcrystalline wax .

The beneficial effects of the present invention are as follows:

The halogen-free flame retardant in the present invention can not only make the flame retardant grade of the resin alloy reach the V1 standard when the added amount is less (accounting for less than 6% by mass of the resin alloy), but also when the halogen-free flame retardant is in the resin alloy When the content in the alloy is more than 20% and less than 30%, the mechanical properties of the resin alloy do not change greatly.

Detailed ways

In order to illustrate the present invention more clearly, the present invention will be further described below with reference to the preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

Example 1

The invention provides a resin alloy, which is composed of the following components: 40 parts by weight of polycarbonate resin, 24 parts by weight of acrylonitrile-butadiene-styrene copolymer, 13 parts by weight of halogen-free flame retardant, 8 parts by weight of additive compatibilizer and 3.6 parts by weight of processing aid; the compatibilizer consists of the following components: 42 parts by weight of diene oligomer, 12 parts by weight of maleic anhydride and 9 parts by weight of acrylic acid; the diene oligomer is composed of 2 parts by weight of butadiene oligomers with a weight-average relative molecular mass of 600-2000 g/mol, 3 parts by weight of pentadiene oligomers with a weight-average relative molecular mass of 1200-3000 g/mol, and 5 parts by weight of relative The molecular weight is 2400-3600g/mol of hexadiene oligomer; the processing aid includes antioxidant, lubricant and mold release agent, and the antioxidant is composed of 1.6 parts by weight of citric acid, 0.8 parts by weight of Tocopherol, 1.6 parts of ascorbic acid and 2.0 parts by weight of phosphite; the lubricant is 1.6 parts by weight of lanthanum stearate, 1.2 parts by weight of zinc stearate, 1.6 parts by weight of polyethylene wax and 0.8 parts by weight of pentaerythritol stearate The mold release agent is a mixture of 0.8 parts by weight of silicone oil mold release agent and 1.6 parts by weight of microcrystalline wax.

Wherein, the halogen-free flame retardant consists of the following components: 6 parts by weight of carbon nanotube nanoparticles, 10 parts by weight of carboxylated carbon nanotube nanoparticles, 6 parts by weight of metal oxide mixture, 28 parts by weight of expandable graphite nanoparticle Granules and 20 parts by weight of a phosphorus-containing halogen-free compound. In this embodiment, the carbon nanotube nanoparticles are composed of 1 part by weight of single-walled carbon nanotube nanoparticles and 5 parts by weight of multi-layered carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are carboxylated monolayers Carbon nanotube nanoparticles, the carboxyl molar fraction of the carboxylated single-wall carbon nanotube nanoparticles is 50-80%, and the metal oxide mixture is composed of 1 part by weight of titanium dioxide nanoparticles, 2 parts by weight of magnesium oxide nanoparticles and 2 parts by weight. Parts by weight of aluminum oxide nanoparticles, the phosphorus-containing non-halide compound is 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane .

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 1.

Example 2

The invention provides a resin alloy, which is composed of the following components: 43 parts by weight of polycarbonate resin, 20 parts by weight of acrylonitrile-butadiene-styrene copolymer, 21 parts by weight of halogen-free flame retardant, 6 parts by weight of additive compatibilizer and 2.4 parts by weight of processing aid; the compatibilizer consists of the following components: 34 parts by weight of diene oligomer, 16 parts by weight of maleic anhydride and 3 parts by weight of acrylic acid; the diene oligomer is composed of 1 part by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 2 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol, and 4 parts by weight of relative The composition of the hexadiene oligomer with a molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant is composed of the following components: 1 part by weight of carbon nanotube nanoparticles, 18 parts by weight of carboxylated carbon nanotube nanoparticles, 9 parts by weight of metal oxide mixture, 40 parts by weight of expandable graphite nanoparticle Granules and 15 parts by weight of a phosphorus-containing halogen-free compound. In this embodiment, the carbon nanotube nanoparticles are composed of 3 parts by weight of single-walled carbon nanotube nanoparticles and 3 parts by weight of multi-layered carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are carboxylated multi-layered Carbon nanotube nanoparticles, the carboxylation mole fraction of the carboxylated multilayer carbon nanotube nanoparticles is 50-60%, and the metal oxide mixture is composed of 1 part by weight of titanium dioxide nanoparticles, 3 parts by weight of magnesium oxide nanoparticles and 2 parts by weight of aluminum oxide nanoparticles, the phosphorus-containing non-halogen compound is tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane-4 - methylene) phosphate.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 2.

Example 3

The invention provides a polyphenylene ether resin alloy, which is composed of the following components: 48 parts by weight of polycarbonate resin, 26 parts by weight of acrylonitrile-butadiene-styrene copolymer, 6 parts by weight of halogen-free flame retardant, 9 parts by weight of Parts by weight of a compatibilizer and 2 parts by weight of a processing aid; the compatibilizer consists of the following components: 48 parts by weight of diene oligomer, 8 parts by weight of maleic anhydride and 11 parts by weight of acrylic acid; the low diene The polymer is composed of 3 parts by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 3 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol and 3 parts by weight The composition of the hexadiene oligomer with a weight average relative molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant consists of the following components: 8 parts by weight of carbon nanotube nanoparticles, 11 parts by weight of carboxylated carbon nanotube nanoparticles, 5 parts by weight of metal oxide mixture, 20 parts by weight of expandable graphite nanoparticle Granules and 26 parts by weight of phosphorus-containing halogen-free compounds. In this embodiment, the carbon nanotube nanoparticles are multi-layer carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are composed of 2 parts by weight of carboxylated single-walled carbon nanotube nanoparticles and 6 parts by weight of carboxylated polystyrene Layered carbon nanotube nanoparticle composition, the carboxylated single-walled carbon nanotube nanoparticle has a carboxyl molar fraction of 50-80%, and the carboxylated multi-layered carbon nanotube nanoparticle has a carboxylated molar fraction of 50-60% , the metal oxide mixture is composed of 2 parts by weight of titanium dioxide nanoparticles, 3 parts by weight of magnesium oxide nanoparticles and 3 parts by weight of aluminum oxide nanoparticles, and the phosphorus-containing non-halogen compound is polyphosphate.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 3.

Example 4

The invention provides a resin alloy, which is composed of the following components: 52 parts by weight of polycarbonate resin, 28 parts by weight of acrylonitrile-butadiene-styrene copolymer, 18 parts by weight of halogen-free flame retardant, 10 parts by weight of additive compatibilizer and 4 parts by weight of processing aid; the compatibilizer consists of the following components: 30 parts by weight of diene oligomer, 15 parts by weight of maleic anhydride and 17 parts by weight of acrylic acid; the diene oligomer is composed of 4 parts by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 2 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol, and 3 parts by weight of relative The composition of the hexadiene oligomer with a molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant is composed of the following components: 3 parts by weight of carbon nanotube nanoparticles, 17 parts by weight of carboxylated carbon nanotube nanoparticles, 8 parts by weight of metal oxide mixture, 38 parts by weight of expandable graphite nanoparticle Granules and 17 parts by weight of phosphorus-containing halogen-free compounds. In this embodiment, the carbon nanotube nanoparticles are single-walled carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are composed of 5 parts by weight of carboxylated single-walled carbon nanotube nanoparticles and 5 parts by weight of carboxylated polystyrene Layered carbon nanotube nanoparticle composition, the carboxylated single-walled carbon nanotube nanoparticle has a carboxyl molar fraction of 50-80%, and the carboxylated multi-layered carbon nanotube nanoparticle has a carboxylated molar fraction of 50-60% , the metal oxide mixture is composed of 2 parts by weight of titanium dioxide nanoparticles, 3 parts by weight of magnesium oxide nanoparticles and 2 parts by weight of aluminum oxide nanoparticles, and the phosphorus-containing halide-free compound is composed of 12 parts by weight of polyphosphate and 6 parts by weight of Tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane-4-methylene)phosphate.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 4.

Example 5

The invention provides a resin alloy, which is composed of the following components: 55 parts by weight of polycarbonate resin, 25 parts by weight of acrylonitrile-butadiene-styrene copolymer, 26 parts by weight of halogen-free flame retardant, 7 parts by weight of additive compatibilizer and 2.8 parts by weight of processing aid; the compatibilizer consists of the following components: 50 parts by weight of diene oligomer, 20 parts by weight of maleic anhydride and 7 parts by weight of acrylic acid; the diene oligomer is composed of 4 parts by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 4 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol, and 5 parts by weight of relative The composition of the hexadiene oligomer with a molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant is composed of the following components: 2 parts by weight of carbon nanotube nanoparticles, 20 parts by weight of carboxylated carbon nanotube nanoparticles, 10 parts by weight of metal oxide mixture, 26 parts by weight of expandable graphite nanoparticle Granules and 30 parts by weight of a phosphorus-containing halogen-free compound. In this embodiment, the carbon nanotube nanoparticles are composed of 6 parts by weight of single-walled carbon nanotube nanoparticles and 3 parts by weight of multi-layered carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are composed of 6 parts by weight of carboxyl groups carboxylated single-walled carbon nanotube nanoparticles and 3 parts by weight of carboxylated multi-layered carbon nanotube nanoparticles, the carboxylated single-walled carbon nanotube nanoparticles have a carboxyl molar fraction of 50-80%, and the The carboxylation mole fraction of the carbon nanotube nanoparticles is 50-60%, the metal oxide mixture is composed of 1 part by weight of titanium dioxide nanoparticles, 1 part by weight of magnesium oxide nanoparticles and 1 part by weight of aluminum oxide nanoparticles, and the containing Phosphorus-free halide consists of 6 parts by weight of tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane-4-methylene)phosphate and 6 1-Oxa-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane in parts by weight.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 5.

Example 6

The invention provides a resin alloy, which is composed of the following components: 60 parts by weight of polycarbonate resin, 30 parts by weight of acrylonitrile-butadiene-styrene copolymer, 30 parts by weight of halogen-free flame retardant, 12 parts by weight of additive compatibilizer and 3.2 parts by weight of processing aid; the compatibilizer is composed of the following components: 32 parts by weight of diene oligomer, 17 parts by weight of maleic anhydride and 15 parts by weight of acrylic acid; the diene oligomer is composed of 3 parts by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 4 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol, and 3 parts by weight of relative The composition of the hexadiene oligomer with a molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant is composed of the following components: 10 parts by weight of carbon nanotube nanoparticles, 13 parts by weight of carboxylated carbon nanotube nanoparticles, 7 parts by weight of metal oxide mixture, 32 parts by weight of expandable graphite nanoparticle Granules and 18 parts by weight of phosphorus-containing halogen-free compounds. In this embodiment, the carbon nanotube nanoparticles are composed of 4 parts by weight of single-walled carbon nanotube nanoparticles and 5 parts by weight of multi-layered carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are composed of 7 parts by weight of carboxyl groups composed of carboxylated single-walled carbon nanotube nanoparticles and 4 parts by weight of carboxylated multi-layered carbon nanotube nanoparticles, the carboxylated single-walled carbon nanotube nanoparticles have a carboxyl molar fraction of 50-80%, and the carboxylated multilayered carbon nanotube nanoparticles The carboxylation mole fraction of the carbon nanotube nanoparticles is 50-60%, the metal oxide mixture is composed of 2 parts by weight of titanium dioxide nanoparticles, 1 part by weight of magnesium oxide nanoparticles and 1 part by weight of aluminum oxide nanoparticles, the containing Phosphorus-free halide consisting of 12 parts by weight polyphosphate and 2 parts by weight tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane-4-idene methyl) phosphate composition.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 6.

Example 7

The invention provides a resin alloy, which is composed of the following components: 54 parts by weight of polycarbonate resin, 28 parts by weight of acrylonitrile-butadiene-styrene copolymer, 24 parts by weight of halogen-free flame retardant, 9.6 parts by weight of additive compatibilizer and 3.3 parts by weight of processing aid; the compatibilizer is composed of the following components: 36 parts by weight of diene oligomer, 16 parts by weight of maleic anhydride and 15.2 parts by weight of acrylic acid; the diene oligomer is composed of 4 parts by weight of butadiene oligomers with a weight average relative molecular mass of 600-2000 g/mol, 2 parts by weight of pentadiene oligomers with a weight average relative molecular mass of 1200-3000 g/mol, and 3 parts by weight of relative The composition of the hexadiene oligomer with a molecular mass of 2400-3600 g/mol; the composition of the processing aid is the same as that of the processing aid in Example 1.

Wherein, the halogen-free flame retardant is composed of the following components: 3.2 parts by weight of carbon nanotube nanoparticles, 17.6 parts by weight of carboxylated carbon nanotube nanoparticles, 7.6 parts by weight of metal oxide mixture, 36 parts by weight of expandable graphite nanoparticle particles and 25.8 parts by weight of phosphorus-containing halogen-free compounds. In this embodiment, the carbon nanotube nanoparticles are composed of 6 parts by weight of single-walled carbon nanotube nanoparticles and 4.2 parts by weight of multi-layered carbon nanotube nanoparticles, and the carboxylated carbon nanotube nanoparticles are composed of 7 parts by weight of carboxyl groups carboxylated single-walled carbon nanotube nanoparticles and 3 parts by weight of carboxylated multi-layered carbon nanotube nanoparticles, the carboxylated single-walled carbon nanotube nanoparticles have a carboxyl molar fraction of 50-80%, and the The carboxylation mole fraction of carbon nanotube nanoparticles is 50-60%, the metal oxide mixture is composed of 1.2 parts by weight of titanium dioxide nanoparticles, 3 parts by weight of magnesium oxide nanoparticles and 2 parts by weight of aluminum oxide nanoparticles, the containing Phosphorus-free halide The phosphorus-containing halide-free compound consists of 12 parts by weight of polyphosphate and 4 parts by weight of 1-oxa-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2, 2,2]octane and 4 parts by weight of tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane-4-methylene)phosphate composition.

When preparing the resin in the present invention by using the formulation of the resin alloy in this example, firstly ultrasonically mixing the halogen-free flame retardant, and then granulating the resin alloy in this example with a twin-screw extruder, thereby obtaining The resin alloy is denoted as alloy 7.

Comparative Example

In this embodiment, the polyphenylene ether resin alloy is composed of the following components: 54 parts by weight of polycarbonate, 28 parts by weight of acrylonitrile-butadiene-styrene copolymer, 24 parts by weight of flame retardant, 8 parts by weight of compatibilizer, 0.2 parts by weight of antioxidant, 0.1 part by weight of auxiliary antioxidant, wherein, the flame retardant is a flame retardant system composed of phosphorus-based flame retardant, nitrogen-based flame retardant, and inorganic hydroxide, and the three The weight ratio is 1:1:1, wherein the phosphorus-based flame retardants are triphenyl phosphate (TPP), tetraphenyl (bisphenol-A) diphosphate (BDP), tetraphenyl resorcinol diphosphate One or more mixtures of phosphoric acid ester (RDP), arylene condensed phosphoric acid ester (PX-200), and coated red phosphorus; nitrogen-based flame retardant is at least one of melamine and melamine urate ; The inorganic hydroxide is at least one of aluminum hydroxide and magnesium hydroxide.

The preparation method of the resin alloy in this example refers to the preparation method of the resin alloy in Example 7, and the prepared resin alloy is recorded as a comparative alloy.

Performance Testing:

The resin alloy materials prepared in the above Examples 1 to 7 and the resin alloy materials prepared in the comparative example were respectively subjected to the performance tests as shown in Table 1. The relevant performance testing methods are as follows:

(1) Tensile strength: Tested according to ISO527 standard, the tensile speed is 50mm/min;

(2) Bending strength: tested according to ISO178 standard, the speed is 2mm/min;

(3) Flexural modulus: tested according to ISO178 standard, the speed is 2mm/min;

(4) Izod notch impact: tested according to ISO180 standard;

(5) Heat distortion temperature: The heat distortion temperature is tested according to ASTM D-648.

(6) Flame retardancy: the flame retardancy is tested according to the UL-94 standard.

(7) Punching experiment: In the punching experiment described, the injection molded part is fixed on the fixture, and a small hole with a diameter of 5mm and a thickness of 32mm is punched. During the whole process of punching, the part is qualified without cracking. If cracking occurs, it is regarded as unqualified.

After testing, the relevant properties of the above-mentioned materials from Examples 1 to 7 and Comparative Examples are shown in Table 1.

Table 1 Performance test results of alloys 1-7 and comparative alloys

As can be seen from the data in Table 1, with the increase of the consumption of the halogen-free flame retardant in the present invention, although the mechanical properties of the resin alloy with polycarbonate and ABS as the main body have decreased, the decrease is not obvious. Moreover, when the amount of halogen-free flame retardant exceeds 20% of the mass of the resin alloy, the mechanical properties of the resin alloy do not drop sharply. When the amount of halogen-free flame retardant in the present invention is 14.6% of the mass of the resin alloy, the flame retardant grade of the resin alloy can reach the V0 level. The reason is that the carbon nanotube nanoparticles and the carboxylated carbon nanotube particles can be The adsorption of metal oxide particles on carbon nanotube nanoparticles is conducive to the dispersion of metal oxides and improves the uniformity of flame retardancy of resin alloys, and titanium dioxide in metal oxides can improve alumina, magnesium oxide and expandable. The synergistic effect between graphite and phosphorus-containing halogen-free compound improves the flame retardant effect of the halogen-free flame retardant in the present invention, can reduce the amount of flame retardant in the resin alloy, and is conducive to ensuring the flame retardancy of the resin alloy. On the premise of improving the mechanical properties of resin alloys. Moreover, the carboxyl groups on the carboxylated carbon nanotube nanoparticles can react with the functional groups in acrylic acid and maleic anhydride, thereby improving the phase between polycarbonate, ABS, diene oligomer, and carbon nanotubes in the resin alloy of the present invention. capacity, improve the uniformity of the mechanical properties of the PC/ABS resin alloy in the present invention, and the addition of diene oligomers is beneficial to improve the crosslinking degree of the PC/ABS resin alloy, thereby ensuring that the addition of halogen-free flame retardants will not Reduce the mechanical properties of PC/ABS resin alloys.

The above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the embodiments of the present invention. For those of ordinary skill in the art, on the basis of the above descriptions, other Changes or changes in different forms cannot be exhaustively listed here, and all obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (8)

1. The halogen-free flame retardant is characterized by comprising the following components: 1-10 parts of carbon nano tube nano particles, 10-20 parts of carboxylated carbon nano tube nano particles, 5-10 parts of metal oxide mixture, 20-40 parts of expandable graphite nano particles and 15-30 parts of phosphorus-containing halogen-free compound; the carbon nano tube nano particles are one or two of single-layer carbon nano tube nano particles and multi-layer carbon nano tube nano particles; the metal oxide mixture is a mixture of titanium dioxide nanoparticles, magnesium oxide nanoparticles, and aluminum oxide nanoparticles.

2. The halogen-free flame retardant of claim 1, wherein the carbon nanotube nanoparticles consist of 1-6 parts by weight of single-walled carbon nanotube nanoparticles and 3-5 parts by weight of multi-walled carbon nanotube nanoparticles.

3. The halogen-free flame retardant of claim 1, wherein the carboxylated carbon nanotube nanoparticles are one or both of carboxylated single-walled carbon nanotube nanoparticles and carboxylated multi-walled carbon nanotube nanoparticles.

4. The halogen-free flame retardant of claim 1, wherein the carboxylated carbon nanotube nanoparticles consist of 2 to 7 parts by weight of carboxylated single-walled carbon nanotube nanoparticles and 3 to 6 parts by weight of carboxylated multi-walled carbon nanotube nanoparticles.

5. The halogen-free flame retardant of claim 4, wherein the carboxylated single-walled carbon nanotube nanoparticles have a carboxyl group molar fraction of 50 to 80 percent and the carboxylated multi-walled carbon nanotube nanoparticles have a carboxyl group molar fraction of 50 to 60 percent.

6. The halogen-free flame retardant according to any of claims 1 to 5, wherein the halogen-free phosphorus-containing compound is any one or more of polyphosphate ester, tris (1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2, 2, 2] octane-4-methylene) phosphate, and 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2, 2, 2] octane.

7. The halogen-free flame retardant according to any of claims 1 to 5, wherein the halogen-free phosphorus-containing compound comprises 10 to 15 parts by weight of polyphosphate, 1 to 6 parts by weight of tris (1-oxo-1-phospha-2, 6, 7-trioxabicyclo [2, 2, 2] octane-4-methylene) phosphate and 2 to 8 parts by weight of 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2, 2, 2] octane.

8. Resin alloy containing the halogen-free flame retardant of any of claims 1 to 7, characterized by consisting of: 40-60 parts of polycarbonate resin, 20-30 parts of acrylonitrile-butadiene-styrene copolymer, 6-30 parts of halogen-free flame retardant, 6-12 parts of compatibilizer and 2-4 parts of processing aid; the compatibilizer consists of the following components: 30-50 parts by weight of diene oligomer, 8-20 parts by weight of maleic anhydride and 3-17 parts by weight of acrylic acid; the diene oligomer consists of 1 to 4 parts by weight of butadiene oligomer with the weight average relative molecular mass of 600-2000g/mol, 2 to 4 parts by weight of pentadiene oligomer with the weight average relative molecular mass of 1200-3000g/mol and 3 to 5 parts by weight of hexadiene oligomer with the weight average relative molecular mass of 2400-3600 g/mol; the processing aid comprises an antioxidant, a lubricant and a release agent, wherein the antioxidant consists of 1.6 parts by weight of citric acid, 0.8 part by weight of tocopherol, 1.6 parts by weight of ascorbic acid and 2.0 parts by weight of phosphite ester; the lubricant is a mixture of 1.6 parts by weight lanthanum stearate, 1.2 parts by weight zinc stearate, 1.6 parts by weight polyethylene wax and 0.8 part by weight pentaerythritol stearate; the mold release agent was a mixture of 0.8 parts by weight of a silicone-oil-type mold release agent and 1.6 parts by weight of microcrystalline wax.