CN103360739B - A kind of phosphorus system synergistic fire retardation PC/ABS alloy material and preparation method thereof - Google Patents

Abstract

The invention discloses a phosphorus-based synergistic flame-retardant PC/ABS alloy material, which is characterized in that the PC/ABS alloy resin is 50.0-94.0wt%, the phosphorus-based flame retardant is 5.0-40.0wt%, and the nitrogen-based flame retardant is 0.0-30.0% wt%, silicon-based synergist 0.0-10.0wt%, compatibilizer 0.5-20.0wt, antioxidant 0.5-1.0wt%; the PC content in the PC/ABS alloy material is 90.0-10.0wt%, and the ABS content is 10.0-90.0wt%, the above components are weight percent. A phosphorus-based synergistic flame-retardant PC/ABS alloy material provided by the present invention is composed of a phosphorus-based flame retardant and a nitrogen-based flame retardant or used in conjunction with a phosphorus-based flame retardant and a silicon-based synergist, and is melt-blended Extrusion method of preparation. On the one hand, it can improve the mechanical, processing, heat resistance and electrical properties of the halogen-free flame-retardant PC/ABS alloy material; on the other hand, it can improve the flame-retardant efficiency of the flame-retardant PC/ABS alloy material and reduce the release of It is an environmentally friendly flame retardant material with low smoke and less toxicity.

Description

A phosphorus-based synergistic flame-retardant PC/ABS alloy material and its preparation method

technical field

The invention belongs to a halogen-free flame-retardant PC/ABS alloy material, in particular to a phosphorus-based synergistic flame-retardant PC/ABS alloy material and a preparation method thereof.

Background technique

Polycarbonate (PC) is a polymer whose molecular chain repeating structural unit is carbonate type. PC has the advantages of high impact strength, good creep resistance and dimensional stability, heat resistance, transparency, low water absorption, non-toxicity, and excellent dielectric properties. Many high-tech fields such as aviation, aerospace, electronic computers, optical fibers and other fields are widely used; however, PC also has disadvantages such as poor processing fluidity, easy stress cracking, sensitivity to notches, easy wear, poor chemical resistance, and high prices. Its application in many fields is limited.

ABS is a blend of acrylonitrile-butadiene-styrene copolymer or acrylonitrile/styrene copolymer and styrene/butadiene copolymer. The English name is Acrylonitrile-Butadiene-Styrene (ABS), which is A mixture of butadiene graft copolymer and acrylonitrile-styrene copolymer, in which acrylonitrile accounts for 15%-35%, butadiene accounts for 5%-30%, and styrene accounts for 40-60%. With the change of the ratio of the three components, the physical and mechanical properties of PC/ABS resin change accordingly. The performance is between general-purpose plastics and engineering plastics. It has good impact resistance and excellent fluidity, but its heat resistance and weather resistance are poor. , the mechanical properties are not ideal, so its application is limited.

The PC/ABS alloy can overcome the shortcomings of the two raw materials and carry forward the advantages of each other. After blending the two, one can improve the heat resistance, impact and tensile strength of PC/ABS, and the other can reduce the polycarbonate. Ester melt viscosity improves processing performance, reduces PC notch sensitivity, improves PC stress cracking, and reduces production costs. Especially because PC/ABS alloy provides better overall cost and excellent low temperature notched impact strength, PC/ABS alloy has been developed and applied rapidly, and its development speed exceeds the development speed of other alloys of ABS and PC. The overall superior heat resistance, strength and processability are the reasons for the rapid development of PC/ABS alloys, so PC/ABS alloys have a broader application market

PC/ABS alloy materials have been widely used in the automotive industry, such as used to make instrument panels, bumpers, body panels, interior and exterior decorations and other components, and can also be used in office machines such as copiers, typewriters and computers. In recent years, in order to meet the special requirements for fire safety in the application fields of electronics and electrical products, PC/ABS alloys must have excellent flame retardant properties, and the flame retardant technology of PC/ABS alloys has become a research hotspot. As people's calls for environmental protection and safety are increasing, the requirements for environmental friendliness of materials are getting higher and higher. At present, the commonly used halogenated flame retardants such as decabromodiphenyl ether will produce toxic and corrosive gases and a large amount of smoke when the material is pyrolyzed and burned, which will pollute the environment and cause secondary pollution. The promulgation of the two directives has restricted the application of traditional halogen-based flame-retardant PC/ABS alloys in many industries. Therefore, under the situation that the call for non-halogenation of flame retardant materials is increasing day by day, researchers at home and abroad have begun to apply various halogen-free flame retardants to PC/ABS alloys, in order to obtain less smoke, low toxicity, high efficiency and environmentally friendly halogen-free flame retardants. PC/ABS alloy products.

At present, the halogen-free flame retardant system of PC/ABS alloy includes phosphorus-containing, nitrogen-based, and silicon-based flame retardants, inorganic flame-retardant systems and intumescent flame-retardant systems. Aluminum hydroxide and magnesium hydroxide are the two most commonly used inorganic flame retardants, which have the advantages of non-toxicity, smoke suppression, and low price. However, the flame retardant efficiency of inorganic powder fillers is low, and it is possible to add more than 40%. Reaching the UL94V-0 flame retardant grade, in addition, the compatibility of inorganic flame retardants with PC/ABS alloys is poor, and a large amount of inorganic fillers seriously reduces the mechanical properties of materials in PC/ABS alloy resins, and the appearance, processability and electrical properties deteriorate sharply. The intumescent flame retardant system mainly includes three elements: acid source, carbon source and gas source. Among them, ammonium polyphosphate, pentaerythritol and melamine are represented, which have the advantages of non-toxicity and smoke suppression, but pentaerythritol has problems of exudation and water solubility. Moreover, the intumescent flame retardant system is incompatible with the polymer, and the mechanical properties and water resistance of the polymer will be reduced after being added, so the application of the intumescent flame retardant system in PC/ABS is also limited.

In the traditional phosphorus-based flame retardant system, when triphenylphosphate (TPP) and its derivatives are applied to PC/ABS alloys, the volatilization temperature of TPP is lower than the processing temperature of PC/ABS alloys, resulting in TPP It is easy to volatilize and seep out during the processing of PC/ABS alloy. The improved tert-butyl phosphate triphenyl phosphate on the basis of TPP is more superior than TPP in flame retardancy. It is a liquid flame retardant with better durability and hydrolytic stability in the resin, and it is not easy to produce surface stress cracks. , but it still has high volatility. Pentaerythritol spirocyclic phosphate (PSDPP) has a very high flame retardant efficiency in PC/ABS alloys. Only adding 3.8% PSDPP and 3.5% TPP is enough to make PC/ABS alloy reach V-0 level. However, the pentaerythritol spirocyclic phosphate flame retardant has high volatility and water solubility, making it difficult to be applied in PC/ABS alloys.

For the above reasons, the selection of phosphorus-based flame retardants with high thermal stability and good water resistance and the introduction of synergists into phosphorus-based flame retardants can effectively improve the flame-retardant efficiency of PC/ABS alloys. Therefore, the present invention uses phosphorus-based flame retardants to flame-retardant PC/ABS alloy materials, and adds nitrogen-based flame retardants or silicon-based synergists to synergistically flame-retardant PC/ABS alloys to reduce the amount of flame retardants. Improve the flame retardant efficiency of phosphorus-based flame-retardant PC/ABS alloy materials.

Contents of the invention

The purpose of the present invention is to provide a phosphorus-based synergistic halogen-free flame-retardant PC/ABS alloy material for the low flame-retardant efficiency of the halogen-free flame retardant to the PC/ABS alloy and poor thermal stability and water resistance. The flame retardant PC/ABS alloy material provided in the article uses phosphorus-based and nitrogen-based flame retardants or phosphorus-based flame retardants and silicon-based synergists to use synergistically. On the one hand, it can improve the flame retardant of halogen-free flame-retardant PC/ABS alloy materials. Efficiency, improve the comprehensive mechanical properties, heat resistance, electrical properties, etc. of halogen-free flame-retardant PC/ABS alloy materials; and reduce the toxic gas released during the combustion process, with low smoke and less toxicity. Therefore, the phosphorus-based synergistic flame-retardant PC/ABS alloy material in the present invention is an environmentally friendly flame-retardant material.

1. A phosphorus-based synergistic flame-retardant PC/ABS alloy material provided by the present invention is characterized in that the material is composed of the following components:

PC/ABS alloy 50.0-94.0wt%

Phosphorus flame retardant 5.0-40.0wt%

Nitrogen flame retardant 0.0-30.0wt%

Silicone synergist 0.0-10.0wt%

Compatibilizer 0.5-20.0wt%

Antioxidant 0.5-1.0wt%

The above components are all percentages by weight, among which the PC/ABS alloy is preferably 60.0-90.0wt%, the phosphorus-based flame retardant is preferably 8.0-25.0wt%, the nitrogen-based flame retardant is preferably 0.0-20.0wt%, and the silicon-based synergist is preferably 0.0-4.0wt%, the compatibilizer is preferably 2.0-15.0wt%, and the antioxidant is preferably 0.5-0.8wt%.

2. In the PC/ABS alloy resin contained in the above phosphorus-based synergistic flame-retardant PC/ABS alloy material, the weight percentage content of PC contained is 90.0-10.0 wt%, and the weight percentage content of ABS is 10.0-90.0 wt%.

3. The phosphorus-based flame retardant contained in the above-mentioned phosphorus-based synergistic flame-retardant PC/ABS alloy material includes one of phosphate, polyphosphate, pyrophosphate, inorganic hypophosphite, and organic hypophosphite.

4. The nitrogen-based flame retardant contained in the phosphorus-based synergistic flame-retardant PC/ABS alloy material includes one of melamine, melamine cyanurate salt, dicyandiamide, melamine and its salt, and guanidine salt.

5. The silicon-based synergists contained in the above-mentioned phosphorus-based synergistic flame-retardant PC/ABS alloy materials include silane, dimethylsiloxane, methylphenylsiloxane, silicone resin, polysilsesquioxane (POSS) in one.

6. The compatibilizers contained in the above phosphorus-based synergistic flame-retardant PC/ABS alloy materials include maleic anhydride grafted polystyrene, glycidyl methacrylate grafted polystyrene, maleic anhydride grafted ABS, methyl Glycidyl acrylate grafted ABS, glycidyl methacrylate grafted polystyrene-butadiene-styrene block copolymer (SBS), maleic anhydride grafted SBS, maleic anhydride grafted rubber, methyl One of glycidyl acrylate graft rubber, ethylene-acrylate copolymer, methacrylate copolymer, ethylene-acrylate-glycidyl methacrylate copolymer

7. The preparation method of a phosphorus-based synergistic flame-retardant PC/ABS alloy material provided by the present invention is a method of melt blending and extrusion, and the specific process and blending conditions are as follows:

(1) Mix the dried flame retardant, synergist, compatibilizer and antioxidant in a high-speed mixer according to the ratio and use it as a compounding agent for flame retardants.

(2) Add the compounding agent of PC/ABS alloy and flame retardant to the twin-screw extruder for melt blending and extrusion. The temperature of each section of the twin-screw extruder is 180-280°C. After melt extrusion Cool and granulate.

detailed description

The present invention is described in detail by the following examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention. Some non-essential improvements and adjustments still belong to the protection scope of the present invention.

Example 1

Put 10.0wt% ammonium polyphosphate, 2.0wt% melamine cyanurate, 2.0wt% SBS grafted maleic anhydride, 0.5wt% antioxidant (0.25wt% 1010 and 0.25wt% 168) into a high-speed mixer After mixing evenly, the compound flame retardant modifier is prepared, and then put into the twin-screw extruder respectively with 85.5wt% PC/ABS alloy resin (weight ratio 70:30), and melt extruded at 200-250°C Take out and cool to granulate. The LOI of the obtained phosphorus-based synergistic flame-retardant PC/ABS alloy material is 26.5%, and the UL94 vertical combustion level is V-0.

Example 2

10.0wt% aluminum methyl phenyl hypophosphite, 2.0wt% dimethyl siloxane, 6.0wt% SBS grafted glyceryl methacrylate, 0.5wt% antioxidant (0.25wt% 1010 and 0.25wt% 168 ) into a high-speed mixer and mixed evenly to prepare a compounded flame retardant modifier, and then mixed with 81.5wt% PC/ABS alloy (weight ratio 70:30), respectively into the twin-screw extruder through the feeding port, Melt and extrude at 200-250°C, and cool to granulate. The LOI of the obtained phosphorus-based synergistic flame-retardant PC/ABS alloy material is 27.0%, and the vertical combustion rating is UL94V-0.

Example 3

Put 15.0wt% aluminum diethyl hypophosphite, 2.0wt% melamine cyanurate, 6.0wt% SBS grafted glycerol methacrylate, 0.5% antioxidant (0.25wt% 1010 and 0.25wt% 168) into After mixing uniformly in a high-speed mixer, the compounded flame retardant modifier was prepared, and then entered into the twin-screw extruder through the feeding port with 81.5.0wt% PC/ABS alloy resin (weight ratio 50:50), respectively. Melt extrusion at 190-240°C, and cool to pelletize. The LOI of the obtained phosphorus-based synergistically flame-retardant PC/ABS alloy material is 27.0, and the UL94 vertical combustion level is V-0.

Example 4

Put 18.0wt% aluminum hypophosphite, 2.0wt% silicone resin, 6.0wt% polystyrene grafted maleic anhydride, 0.5% antioxidant (0.25wt% 1010 and 0.25wt% 168) into a high-speed mixer and mix well Finally, the compounded flame retardant modifier was prepared, and then mixed with 73.5wt% PC/ABS alloy resin (weight ratio 50:50), respectively entered into the twin-screw extruder through the feeding port, and melted at 190-240°C Extrude and cool to granulate. The LOI of the obtained halogen-free flame-retardant PC/ABS alloy material is 26.5, and the UL94 vertical combustion level is V-0.

Example 5

Put 20.0wt% aluminum diethyl hypophosphite, 2.0wt% polysilsesquioxane (POSS), 6.0wt% ABS grafted glyceryl methacrylate, 0.5wt% antioxidant into a high-speed mixer and mix evenly Finally, the compounded flame retardant modifier is prepared, and then mixed evenly with 71.5wt% PC/AB alloy resin (weight ratio 30:70), added to a twin-screw extruder, and melted and extruded at 180-230°C. And cooling granulation. The LOI of the obtained halogen-free flame-retardant PC/ABS alloy material is 26.0, and the UL94 vertical combustion level is V-0.

Example 6

Put 22.0wt% ammonium polyphosphate, 6.0wt% melamine cyanurate, 4.0wt% SBS alloy grafted glycerol methacrylate, 0.5wt% antioxidant (0.25wt% 1010 and 0.25wt% 168) into the high-speed After mixing uniformly in the mixer, the compounded flame retardant modifier was prepared, and then mixed with 67.5wt% PC/ABS alloy resin (weight ratio 30:70), respectively into the twin-screw extruder through the feed port, at 180- Melt extruded at 230°C, cooled and granulated. The LOI of the obtained phosphorus-based synergistic flame-retardant PC/ABS alloy material is 25.0%, and the UL94 vertical combustion level is V-1.

Claims (3)

1. phosphorus system synergistic fire retardation PC/ABS alloy material, it is characterised in that this material is made up of following component:

PC/ABS alloy resin 60.0-90.0wt%, the composition of described PC/ABS alloy resin includes PC content 70.0-30.0wt%, ABS content 30.0-70.0wt%；The consumption of phosphorus flame retardant is 0.39 times of ABS content, 0.40 times, 0.41 times, 0.47 times or 0.49 times, bulking agent 2.0-15.0wt%, antioxidant 0.5-0.8wt%, additionally possibly together with synergistic flame retardant, described synergistic flame retardant is the one in nitrogenated flame retardant 2-6wt% or silicon system synergist 2wt%；

Above constituent content sum is 100%；

Contained phosphorus flame retardant includes phosphate, Quadrafos, any one in pyrophosphate, inorganic hypophosphites, organic hypophosphites；

Contained nitrogenated flame retardant includes any one in tripolycyanamide, MCA, dicyandiamide, melamine and guanidinesalt thereof；

Contained silicon system synergist is any one in silane, dimethyl siloxane, methyl phenyl siloxane, silicones, polysilsesquioxane。

2. phosphorus system according to claim 1 synergistic fire retardation PC/ABS alloy material, it is characterized in that contained bulking agent is maleic anhydride grafted polystyrene, glycidyl methacrylate graft polystyrene, maleic anhydride grafted ABS, glycidyl methacrylate graft ABS, glycidyl methacrylate graft SBS, Maleic anhydride-containg polyethylene, maleic anhydride graft rubber, glycidyl methacrylate graft rubber, vinyl-acrylate copolymer, methacrylate copolymer, any one in ethylene-acrylate-glycidyl methacrylate copolymer。

3. the preparation method of phosphorus system according to claim 1 synergistic fire retardation PC/ABS alloy material is the method adopting melt blending extrusion, concrete technical process:

(1) using dried fire retardant, synergistic flame retardant, bulking agent, antioxidant by proportioning in high-speed mixer mix homogeneously as the built agent of fire retardant；

(2) after the built agent mix homogeneously of PC/ABS alloy resin and fire retardant, joining melt blending extrusion in double screw extruder, the temperature range that double screw extruder is each section is 180-280 DEG C, melt extrudes rear cooling granulation。