CN111440437A - Acid-alkali-resistant high-flame-retardant polyamide composite material and preparation method thereof - Google Patents
Acid-alkali-resistant high-flame-retardant polyamide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an acid-base-resistant high-flame-retardant polyamide composite material which comprises, by weight, 100 parts of flame-retardant semi-aromatic polyamide, 2-5 parts of mineral filler, 2-8 parts of a composite flame retardant and 0.5-1 part of an acid and alkali resistant agent, wherein the composite flame retardant is prepared by mixing diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate according to a mass ratio of 1.5-3:1:0.2-0.5, the acid and alkali resistant agent is sericite powder with a particle size of 400-800 meshes, and the mineral filler is titanium dioxide subjected to organic matter surface treatment or titanium dioxide subjected to hydrated inorganic matter surface treatment.
Description
Technical Field
The invention belongs to the technical field of polyamide engineering plastics, and particularly relates to an acid-alkali-resistant high-flame-retardant polyamide composite material and a preparation method thereof.
Background
Conventional polyamides represented by nylon 6 and nylon 66 have been used in a wide range of applications such as automobile parts, electric and electronic parts, and sliding parts because they have excellent properties such as heat resistance, chemical resistance, rigidity, sliding properties, and moldability, and exhibit extremely high toughness in a hygroscopic state. In the field of automobile industry, polyamide materials are also widely used for interior and exterior trim parts, functional parts and structural parts. The lightweight automobile engine cover has the advantages that the lightweight automobile engine cover is used as the development trend of automobile materials, more and more plastic parts are formed on parts under the automobile engine cover, the diesel engine replaces a gasoline engine or turbocharging replaces mechanical supercharging, the air inflow and the combustion efficiency of the engine are improved, the engine is required to be capable of withstanding higher pressure and temperature, and meanwhile, the lightweight automobile engine cover has excellent flame retardant performance.
The commonly used preparation methods for the flame retardant polyamide 6 at present are a blending method and a polymerization method, wherein the polymerization method comprises a copolymerization method and an in-situ polymerization method. The blending method has the advantages of simple processing technology, high flame retardant addition amount, uneven dispersion and easy precipitation, and has great influence on the mechanical properties of the material. Copolymerization flame-retardant modification is an important flame-retardant modification mode, the research on preparation of flame-retardant polyamide by a copolymerization method is less, the flame-retardant process of the copolymerization method is complex, and the mechanical property of the polyamide is greatly reduced when the addition amount is large. In the in-situ polymerization method, a flame retardant is introduced and dispersed among matrix molecular chains in the synthesis process of a polymer, so that the degradation caused by secondary processing by a blending method can be effectively avoided, but the addition amount required for achieving the flame retardant purpose is large, and the problems of easy precipitation of the flame retardant and poor washing resistance exist, particularly the problems of easy precipitation of the flame retardant in the fiber drafting process, poor flame retardant effect, reduced fiber mechanical properties, rough hand feeling and the like exist when the in-situ polymerization method is applied to the fiber field. The reaction type phosphorus flame retardant is mainly used for gas-phase flame retardance in the process of preparing the flame-retardant polyamide 6 by a polymerization method, has a certain flame-retardant effect, but has weak capability of crosslinking the polyamide into carbon, has serious melt dripping phenomenon and often causes the problems of scald or secondary fire. The flame retardant polyamide 6 prepared by the additive phosphorus flame retardant through a blending method mainly has a condensed phase flame retardant effect, a plurality of phosphorus flame retardants need large addition amount to achieve a good flame retardant effect, the mechanical property is seriously reduced, and the application field of the flame retardant polyamide is further influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the acid-alkali-resistant high-flame-retardance polyamide composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acid-alkali-resistant high-flame-retardant polyamide composite material comprises the following components in parts by weight: 100 parts of flame-retardant semi-aromatic polyamide; 2-5 parts of mineral filler, 2-8 parts of composite flame retardant and 0.5-1 part of acid and alkali resistant agent; in the flame-retardant semi-aromatic polyamide, 60-100 mol% of dicarboxylic acid units are aromatic dicarboxylic acid units, and 70-100 mol% of diamine units are aliphatic diamine units with 9-13 carbon atoms; the dicarboxylic acid unit is terephthalic acid or terephthalic acid and other diacid, wherein the terephthalic acid accounts for 70-100 mol%;
the composite flame retardant is obtained by mixing diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate according to the mass ratio of 1.5-3:1:0.2-0.5, the acid and alkali resistant agent is sericite powder, and the particle size is 400-800 meshes;
the mineral filler is titanium dioxide subjected to surface treatment by organic matters or hydrated inorganic matters, and the dosage of the organic matters or the hydrated inorganic matters is 1-5% of the weight of the titanium dioxide.
The polyamide composite material with acid and alkali resistance and high flame retardance firstly adopts flame-retardant semi-aromatic polyamide, and has a certain flame-retardant function on main raw materials, wherein 60-100 mol% of dicarboxylic acid units in the flame-retardant semi-aromatic polyamide are aromatic dicarboxylic acid units, 70-100 mol% of diamine units are aliphatic diamine units with 9-13 carbon atoms, and the initial unit selection ensures that the finally synthesized semi-aromatic polyamide has certain flame retardance.
The semi-aromatic polyamide or the polyamide resin composition containing the semi-aromatic polyamide of the present invention can be suitably used for various molded articles such as injection molded articles and extrusion molded articles. The semi-aromatic polyamide of the present invention is excellent not only in adhesion to other materials and compatibility with polymer alloys of other materials, but also in mechanical strength, low water absorption, dimensional stability, retention stability and other properties. Therefore, the molded article containing the semi-aromatic polyamide of the present invention or the polyamide resin composition containing the semi-aromatic polyamide of the present invention can be used in a wide range of applications such as electric/electronic materials, automobile parts, production materials, industrial materials, and household goods, and is particularly suitable for use in automobile parts.
The composite flame retardant is preferably prepared by mixing diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate according to the mass ratio of 2:1:0.4, and the selection of the components and the content ratio of the composite flame retardant are obtained through long-term experimental adjustment by the inventor, so that the composite flame retardant is low in addition amount and excellent in flame retardant effect.
Preferably, the titanium dioxide subjected to organic surface treatment is formed by coating the organic coupling agent on the surface of the titanium dioxide through chemical bonding, and then connecting and coating the organic surface modifier and the organic coupling agent through chemical acting force. Further preferably, the organic coupling agent is an organosiloxane compound and a titanate compound, and the organic surface modifier is one of a C1-8 olefin unsaturated monomer, a higher aliphatic metal salt, a higher aliphatic amide and a C1-8 alkyl acrylate.
Preferably, the hydrous inorganic surface-treated titanium dioxide is formed by coating a hydrous inorganic, which is one of hydrous sodium silicate, hydrous aluminum compound, hydrous zirconium compound and hydrous zinc compound, on the surface of titanium dioxide by using a milling method, a coprecipitation method or a co-oxidation method.
In the present invention, it is preferable that the aliphatic diamine unit having 9 to 13 carbon atoms is a 1, 9-nonanediamine unit and/or a 2-methyl-1, 8-octanediamine unit.
Preferably, the dicarboxylic acid unit is terephthalic acid or terephthalic acid and other diacids, and the other diacids are one or more of oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 2-methylsuberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, and cyclohexanedicarboxylic acid.
The polyamide composite material according to the present invention may further comprise other auxiliaries, i.e. auxiliaries conventionally used in the art. Specifically, the auxiliary agent may be at least one selected from toner, antioxidant, lubricant, and anti-ultraviolet agent. The toner is at least one selected from azo complex, amidoketone, naphthone, pyridine anthrone, pteridine, bismuth vanadate, perylene, phthalocyanine blue, phthalocyanine green, anthraquinone, ultramarine violet, pyrene ketone, metal complex, titanium dioxide, zinc sulfide, aniline black, carbon black and azo orange.
Specifically, the preparation method of the polyamide composite material comprises the following steps: uniformly mixing the flame-retardant semi-aromatic polyamide, the mineral filler, the composite flame retardant and the acid-base resistant agent, and extruding and granulating by a double-screw extruder, wherein the extrusion temperature is as follows: 300 ℃ and 350 ℃, and the rotating speed is as follows: 500-600 rpm, obtaining the polyamide composite material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the acid-base-resistant high-flame-retardance polyamide composite material, the flame-retardant semi-aromatic polyamide is utilized, and the composite flame retardant and the mineral filler are selected and used in a matched manner, so that the flame retardant is uniformly dispersed and is not easy to separate out, and the overall flame-retardant effect is good; the sericite powder with the particle size of 400-plus 800 meshes is selected as the acid and alkali resistant agent, so that the acid and alkali resistant performance is excellent.
2. According to the acid-base-resistant high-flame-retardant polyamide composite material, composite flame retardants of diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate are adopted, and experiments show that the flame retardant effect of the mixture of the three flame retardants is better than that of the mixture of the three flame retardants used alone, so that the synergistic flame retardant effect is achieved.
3. In the acid-base-resistant and high-flame-retardant polyamide composite material, the filler is titanium dioxide subjected to organic surface treatment or titanium dioxide subjected to hydrated inorganic surface treatment, so that the wettability of the titanium dioxide in the polymer composite material is improved, and the dispersibility and stability of the titanium dioxide in the polymer are greatly improved. In addition, in the processing process, the dispersibility and uniformity of the composite flame retardant can be improved to a certain degree, so that the mechanical properties of the polyamide composite material are finally improved, and the polyamide composite material can withstand higher pressure and temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the embodiments.
The raw materials used in the invention are all commercially available.
Example 1:
the preparation method of the flame-retardant semi-aromatic polyamide comprises the following steps.
Terephthalic acid according to a molar ratio: 1, 5-glutaric acid: 1, 9-nonanediamine = 1: 0.05: 1, weighing and adding materials, and then sequentially adding sodium hypophosphite and deionized water into a high-temperature high-pressure reaction kettle, wherein the adding amount is 0.5 percent of the mass fraction of the sodium hypophosphite, and the mass fraction of reaction monomers (terephthalic acid, 1, 5-glutaric acid and 1, 9-nonanediamine) is 15 percent. After the atmosphere in the reactor is nitrogen gas through the aeration, the temperature is raised to 180 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 210 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 250 ℃ for constant temperature reaction for 1 hour, the water is drained for about 0.5 hour, and the materials are discharged and granulated. And putting the granulated material into a rotary drum, vacuumizing to ensure that the pressure is lower than 3000Pa, heating to 250-260 ℃, reacting for 3 hours, stopping heating, and discharging after the temperature returns to the room temperature to obtain the flame-retardant semi-aromatic polyamide.
The preparation method of the acid-base-resistant high-flame-retardant polyamide composite material comprises the steps of uniformly mixing 100Kg of flame-retardant semi-aromatic polyamide, 2Kg of mineral filler, 2Kg of composite flame retardant (diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate are mixed according to the mass ratio of 1.5:1: 0.2) and 0.5Kg of sericite powder (400 meshes), and extruding and granulating through a double-screw extruder at the extrusion temperature of 300-350 ℃ and the rotation speed of 500-600 rpm to obtain the polyamide composite material.
The mineral filler is titanium dioxide subjected to surface treatment by a hydrated inorganic substance, and is formed by coating the hydrated inorganic substance on the surface of the titanium dioxide by using a grinding method, a coprecipitation method or a co-oxidation method, wherein the hydrated inorganic substance is one of hydrated sodium silicate, hydrated aluminum compound, hydrated zirconium compound and hydrated zinc compound, and the dosage of the hydrated inorganic substance is 2% of the weight of the titanium dioxide.
Example 2:
the preparation method of the flame-retardant semi-aromatic polyamide comprises the following steps.
Terephthalic acid according to a molar ratio: 2-methyl-1, 8-octanediamine = 1: 1, weighing and adding materials, and then sequentially adding sodium hypophosphite and deionized water into a high-temperature high-pressure reaction kettle, wherein the adding amount is 0.5 percent of the mass fraction of the sodium hypophosphite, and the mass fraction of reaction monomers (terephthalic acid and 2-methyl-1, 8-octanediamine) is 15 percent. After the atmosphere in the reactor is nitrogen gas through the aeration, the temperature is raised to 180 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 210 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 250 ℃ for constant temperature reaction for 1 hour, the water is drained for about 0.5 hour, and the materials are discharged and granulated. And putting the granulated material into a rotary drum, vacuumizing to ensure that the pressure is lower than 3000Pa, heating to 250-260 ℃, reacting for 3 hours, stopping heating, and discharging after the temperature returns to the room temperature to obtain the flame-retardant semi-aromatic polyamide.
The preparation method of the acid-alkali-resistant high-flame-retardant polyamide composite material comprises the steps of uniformly mixing 100Kg of flame-retardant semi-aromatic polyamide, 5Kg of mineral filler, 8Kg of composite flame retardant (diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate are mixed according to the mass ratio of 3:1: 0.5) and 1Kg of sericite powder (800 meshes), and then extruding and granulating through a double-screw extruder at the extrusion temperature of 300-350 ℃ and the rotation speed of 500-600 rpm to obtain the polyamide composite material.
The mineral filler is titanium dioxide subjected to organic surface treatment, the organic coupling agent is coated on the surface of the titanium dioxide by chemical bonding, and then the organic surface modifier is coated and connected with the organic coupling agent by chemical acting force. The organic coupling agent is an organosiloxane compound and a titanate compound, and the organic surface modifier is a high-grade aliphatic metal salt, and the using amount of the organic surface modifier is 5% of the weight of the titanium dioxide.
Example 3:
the preparation method of the flame-retardant semi-aromatic polyamide comprises the following steps.
Terephthalic acid according to a molar ratio: 1, 4-succinic acid: 1, 9-nonanediamine = 1: 0.08: 1, weighing and feeding, and then sequentially adding sodium hypophosphite and deionized water into a high-temperature high-pressure reaction kettle, wherein the addition amount is 0.5 percent of the mass fraction of the sodium hypophosphite, and the mass fraction of reaction monomers (terephthalic acid, 1, 4-succinic acid and 1, 9-nonanediamine) is 15 percent. After the atmosphere in the reactor is nitrogen gas through the aeration, the temperature is raised to 180 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 210 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 250 ℃ for constant temperature reaction for 1 hour, the water is drained for about 0.5 hour, and the materials are discharged and granulated. And putting the granulated material into a rotary drum, vacuumizing to ensure that the pressure is lower than 3000Pa, heating to 250-260 ℃, reacting for 3 hours, stopping heating, and discharging after the temperature returns to the room temperature to obtain the flame-retardant semi-aromatic polyamide.
The preparation method of the acid-base-resistant high-flame-retardant polyamide composite material comprises the steps of uniformly mixing 100Kg of flame-retardant semi-aromatic polyamide, 4Kg of mineral filler, 5Kg of composite flame retardant (diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate are mixed according to the mass ratio of 2:1: 0.4) and 0.8Kg of sericite powder (600 meshes), and then extruding and granulating through a double-screw extruder at the extrusion temperature of 300-350 ℃ and the rotation speed of 500-600 rpm to obtain the polyamide composite material.
The mineral filler is titanium dioxide subjected to organic surface treatment, the organic coupling agent is coated on the surface of the titanium dioxide by chemical bonding, and then the organic surface modifier is coated and connected with the organic coupling agent by chemical acting force. The organic coupling agent is an organosiloxane compound and a titanate compound, the organic surface modifier is C1-8 alkyl acrylate, and the using amount of the organic surface modifier is 3% of the weight of titanium dioxide.
Example 4:
the preparation method of the flame-retardant semi-aromatic polyamide comprises the following steps.
Terephthalic acid according to a molar ratio: 1, 4-succinic acid: 2-methyl-1, 8-octanediamine = 1: 0.06: 1, weighing and adding materials, and then sequentially adding sodium hypophosphite and deionized water into a high-temperature high-pressure reaction kettle, wherein the adding amount is that the mass fraction of the sodium hypophosphite is 0.5%, and the mass fraction of reaction monomers (terephthalic acid, 1, 4-succinic acid and 2-methyl-1, 8-octanediamine) is 15%. After the atmosphere in the reactor is nitrogen gas through the aeration, the temperature is raised to 180 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 210 ℃ for constant temperature reaction for 1 hour, the temperature is continuously raised to 250 ℃ for constant temperature reaction for 1 hour, the water is drained for about 0.5 hour, and the materials are discharged and granulated. And putting the granulated material into a rotary drum, vacuumizing to ensure that the pressure is lower than 3000Pa, heating to 250-260 ℃, reacting for 3 hours, stopping heating, and discharging after the temperature returns to the room temperature to obtain the flame-retardant semi-aromatic polyamide.
The preparation method of the acid-alkali-resistant high-flame-retardant polyamide composite material comprises the steps of uniformly mixing 100Kg of flame-retardant semi-aromatic polyamide, 3Kg of mineral filler, 6Kg of composite flame retardant (diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate are mixed according to the mass ratio of 2:1: 0.3) and 1Kg of sericite powder (400 meshes), and then extruding and granulating through a double-screw extruder at the extrusion temperature of 300-350 ℃ and the rotation speed of 500-600 rpm to obtain the polyamide composite material.
The mineral filler is titanium dioxide subjected to organic surface treatment, the organic coupling agent is coated on the surface of the titanium dioxide by chemical bonding, and then the organic surface modifier is coated and connected with the organic coupling agent by chemical acting force. The organic coupling agent is an organosiloxane compound and a titanate compound, the organic surface modifier is high-grade aliphatic amide, and the using amount of the organic surface modifier is 1 percent of the weight of the titanium dioxide.
Comparative example 1:
in comparison with example 1, a polyamide composite material was prepared by purchasing commercially available nylon 6 instead of the flame-retardant semi-aromatic polyamide, and the other operations were the same as in example 1.
Comparative example 2:
in comparison with example 1, the procedure was the same as in example 1 except that no mineral filler was added.
Comparative example 3:
compared with the example 1, the acid and alkali resistant agent sericite powder is not added, and other operations are the same as the example 1.
Comparative example 4:
in comparison with example 1, a commercially available melamine phosphate flame retardant was purchased in place of the composite flame retardant, and the other operations were the same as in example 1.
Performance testing
The end groups and the relative viscosity of the flame-retardant semi-aromatic polyamide in the above examples were tested, and the mechanical properties, acid and alkali resistance and flame retardancy of the acid and alkali resistant highly flame-retardant polyamide composite materials prepared in the above examples and comparative examples were tested. The performance test methods are as follows.
Flame-retardant semi-aromatic polyamide:
(1) end group, adopting a potentiometric titrator to measure the content of amino and carboxyl end groups of a polymer, weighing 0.45g of polyamide, adding 50m L of preheated and melted o-cresol, heating and refluxing until the sample is dissolved, placing the polyamide in a 50 ℃ water tank to cool to 50 ℃, adding 0.5m L of formaldehyde solution, putting the polyamide in a magneton stirring solution, immersing an electrode testing part of the fully-automatic potentiometric titrator in the solution, titrating the test end carboxyl data by using a calibrated KOH-ethanol solution, weighing 0.45g of the polyamide, adding 45m L of phenol and 3m L of anhydrous methanol, heating and refluxing until the sample is dissolved, placing the polyamide in the 50 ℃ water tank to cool to 50 ℃, putting the polyamide in the magneton stirring solution, immersing the electrode testing part of the fully-automatic potentiometric titrator in the solution, and titrating the test end amino data by using a calibrated hydrochloric acid standard solution.
(2) Relative viscosity the relative viscosity of the product was measured at a concentration of 0.25g/d L in 98% concentrated sulfuric acid at (25. + -. 0.01) ℃ using an Ubbelohde viscometer, according to standard GB/T12006.1-1989.
The molecular weight of the polyamide is judged according to the end group content and the relative viscosity of the polyamide, and the molecular weight of the polyamide is similar if the relative viscosity and the end group content are similar under the premise of the same monomer.
Acid and alkali resistant high flame retardant polyamide composite material:
(3) tensile strength: the tensile strength of the resin material is measured with reference to standard ISO 527.
(4) Bending strength: referring to standard ISO 178, the bending strength of the resin material is examined.
(5) Notched impact strength/unnotched impact strength: the impact strength of the resin material was examined with reference to standard ISO 180.
(6) U L94 flame retardant rating.A specimen size of 13cm × 1.3cm × 0.3.3 cm was determined with reference to GB/T2408-1996.
(7) Limiting oxygen index (L OI) determined with reference to the GB/T5454-1997 standard, the specimen size being 12cm × 1cm × 0.4 cm.
(8) The acid and alkali resistance is determined according to the specification of 6.11 in GB/T17748-1999, and the test result is the worst performance of three samples, wherein the size of the sample is 10cm × 10cm × 0.3 cm.
Table 1 results of performance testing
According to the self-made flame-retardant semi-aromatic polyamide, the monomer raw materials have a certain flame-retardant function, and the amount of the optimized composite flame retardant is adjusted, so that the flame retardant is uniformly dispersed and is difficult to separate out, and the whole flame-retardant effect is good. Meanwhile, through the treatment of the filler, the dispersibility and the stability of the filler are greatly improved in the polymer, and the dispersibility and the uniformity of the composite flame retardant can also be improved to a certain extent in the processing process, so that the mechanical property of the polyamide composite material is finally improved, and the polyamide composite material can bear higher pressure and temperature. The acid and alkali resistance of the polyamide composite material is improved by adding the acid and alkali resistance agent. As can be seen from Table 1, the polyamide composite material prepared by the invention has good mechanical properties, excellent flame retardance and acid and alkali resistance.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The acid-alkali-resistant high-flame-retardant polyamide composite material is characterized by comprising the following components in parts by weight: 100 parts of flame-retardant semi-aromatic polyamide; 2-5 parts of mineral filler, 2-8 parts of composite flame retardant and 0.5-1 part of acid and alkali resistant agent; in the flame-retardant semi-aromatic polyamide, 60-100 mol% of dicarboxylic acid units are aromatic dicarboxylic acid units, and 70-100 mol% of diamine units are aliphatic diamine units with 9-13 carbon atoms; the dicarboxylic acid unit is terephthalic acid or terephthalic acid and other diacid, wherein the terephthalic acid accounts for 70-100 mol%;
the composite flame retardant is obtained by mixing diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate according to the mass ratio of 1.5-3:1:0.2-0.5, the acid and alkali resistant agent is sericite powder, and the particle size is 400-800 meshes;
the mineral filler is titanium dioxide subjected to surface treatment by organic matters or hydrated inorganic matters, and the dosage of the organic matters or the hydrated inorganic matters is 1-5% of the weight of the titanium dioxide.
2. The acid and alkali resistant and high flame retardant polyamide composite material as claimed in claim 1, wherein the composite flame retardant is obtained by mixing diethyl aluminum hypophosphite, tris (β -chloroethyl) phosphate and zinc borate according to a mass ratio of 2:1: 0.4.
3. The acid and alkali resistant and high flame retardant polyamide composite material as claimed in claim 1, wherein the titanium dioxide subjected to organic surface treatment is formed by coating an organic coupling agent on the surface of the titanium dioxide through chemical bonding, and then coating an organic surface modifier through chemical action and the organic coupling agent.
4. The acid and alkali resistant and flame retardant polyamide composite material as claimed in claim 3, wherein the organic coupling agent is an organosiloxane compound and a titanate compound, and the organic surface modifier is one of a C1-8 olefinic unsaturated monomer, a higher aliphatic metal salt, a higher aliphatic amide and a C1-8 alkyl acrylate.
5. The acid and alkali resistant and flame retardant polyamide composite material as claimed in claim 1, wherein the hydrated inorganic surface-treated titanium dioxide is formed by coating a hydrated inorganic material on the surface of titanium dioxide by using a grinding method, a co-precipitation method or a co-oxidation method, and the hydrated inorganic material is one of hydrated sodium silicate, hydrated aluminum compound, hydrated zirconium compound and hydrated zinc compound.
6. The acid and alkali resistant and high flame retardant polyamide composite material as claimed in claim 1, wherein the aliphatic diamine unit having 9 to 13 carbon atoms is 1, 9-nonanediamine unit and/or 2-methyl-1, 8-octanediamine unit.
7. The acid and alkali resistant high flame retardant polyamide composite material of claim 1, wherein the other diacid is one or more of oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 2-methylsuberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid, 1, 14-tetradecanedioic acid, and cyclohexanedicarboxylic acid.
8. The acid and alkali resistant and flame retardant polyamide composite material as claimed in claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is at least one selected from toner, antioxidant, lubricant and anti-ultraviolet agent.
9. The acid and alkali resistant and flame retardant polyamide composite material as claimed in claim 8, wherein the toner is at least one selected from azo complex, aminoketone, naphthone, pyridanthone, pteridine, bismuth vanadate, perylene, phthalocyanine blue, phthalocyanine green, anthraquinone, ultramarine violet, pyreneketone, metal complex, titanium dioxide, zinc sulfide, aniline black, carbon black, and azo orange.
10. A method for producing a polyamide composite material as claimed in any one of claims 1 to 9, characterized by comprising the steps of: uniformly mixing the flame-retardant semi-aromatic polyamide, the mineral filler, the composite flame retardant and the acid-base resistant agent, and extruding and granulating by a double-screw extruder, wherein the extrusion temperature is as follows: 300 ℃ and 350 ℃, and the rotating speed is as follows: 500-600 rpm, obtaining the polyamide composite material.
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