Hygrothermal-aging-resistant flame-retardant glass fiber reinforced PC (polycarbonate) material, preparation method and application

Abstract

The invention relates to the technical field of high polymer materials, in particular to a damp-heat-aging-resistant flame-retardant glass fiber reinforced PC material, a preparation method and application. The PC material is prepared from the following components in parts by weight: 70 to 80 parts of polycarbonate resin, 10 to 20 parts of glass fiber, 5 to 10 parts of a flame retardant, 5 to 10 parts of a toughening agent, 0.1 to 0.5 part of an antioxidant, 0.4 to 1 part of a lubricant, 0.3 to 0.8 part of an anti-dripping agent, 0.1 to 1 part of a light stabilizer and 0.1 to 1 part of an anti-ultraviolet agent. Wherein the flame retardant is a compound system of an organophosphorus flame retardant and an inorganic flame retardant, and the mass ratio of the organophosphorus flame retardant to the inorganic flame retardant is (1-3): (2-4); the antioxidant is a compound system of a hindered phenol antioxidant and a phosphite ester antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite ester antioxidant is (1-2): 1. By compounding the organic phosphorus flame retardant and the inorganic flame retardant, efficient flame retardance of the PC material is realized, and meanwhile, the negative influence of a single flame retardant on the performance of the PC material is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a flame-retardant glass fiber reinforced PC material resistant to moisture and heat aging, a preparation method and application thereof. Background Art

[0002] Polycarbonate (PC) materials are widely used in the fields of automobiles, electronic appliances, and construction due to their excellent mechanical properties, electrical properties, thermal stability, and good processing properties. However, PC materials are prone to aging during use, especially in hot and humid environments, which leads to a decrease in performance and even affects the service life of the product. In addition, the flame retardant properties of PC materials need to be improved to meet higher safety requirements.

[0003] In order to improve the hygrothermal aging and flame retardant properties of PC materials, people usually add flame retardants and reinforcing agents to PC materials. However, traditional flame retardants and reinforcing agents often have adverse effects on the performance of PC materials, such as reducing their mechanical properties or processing properties. Therefore, developing a preparation method that can not only improve the flame retardant properties of PC materials but also enhance their hygrothermal aging properties has important practical significance and application value. Summary of the invention

[0004] In view of the shortcomings of the prior art, the purpose of the present invention can be achieved through the following technical solutions:

[0005] A flame-retardant glass fiber reinforced PC material resistant to moisture and heat aging, wherein the raw materials for preparing the PC material include the following components in parts by weight:

[0006] 70-80 parts of polycarbonate resin, 10-20 parts of glass fiber, 5-10 parts of flame retardant, 5-10 parts of toughening agent, 0.1-0.5 parts of antioxidant, 0.4-1 parts of lubricant, 0.3-0.8 parts of anti-dripping agent, 0.1-1 parts of light stabilizer and 0.1-1 parts of anti-ultraviolet agent;

[0007] The flame retardant is a composite system of a phosphorus-containing compound and an inorganic flame retardant, and the mass ratio of the phosphorus-containing compound to the inorganic flame retardant is (1-3):(2-4); the phosphorus-containing compound is selected from at least one of hexaphenoxycyclotriphosphazene, triphenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl phosphate)], and triphenylphosphine oxide, and the inorganic flame retardant is selected from at least one of potassium perfluorobutyl sulfonate, potassium benzenesulfonylbenzenesulfonate, sodium p-toluenesulfonate, and sodium trichlorophenyl sulfonate;

[0008] The antioxidant is a compound system of a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (1-2):1.

[0009] Furthermore, the polycarbonate is at least one of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate and silicone-modified polycarbonate; the density of the polycarbonate is 1.19-1.21 g / cm 3 , melt index is 7-22g / 10min.

[0010] Furthermore, the toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylic ester copolymer, acrylonitrile-styrene-acrylate copolymer and silicone rubber graft copolymer.

[0011] Furthermore, the light stabilizer is at least one of salicylates, benzoates, benzophenones, benzotriazoles, substituted acrylonitriles, oxamides, organic nickel complexes and hindered amine ultraviolet absorbers.

[0012] Furthermore, the lubricant is at least one of polyethylene wax, calcium stearate and silicone.

[0013] Furthermore, the anti-dripping agent is at least one of SAN-coated polytetrafluoroethylene or MMA-coated polytetrafluoroethylene.

[0014] A method for preparing a highly flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging, the method comprising the following steps:

[0015] S1. Evenly mix PC resin, flame retardant, antioxidant, compatibilizer and coupling agent to obtain a premix;

[0016] S2, melt-blending the premix and the glass fiber to obtain a melt blend;

[0017] S3, melting and granulating the molten blend to obtain a flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging.

[0018] The above-mentioned flame-retardant glass fiber reinforced PC material resistant to moisture and heat aging is used in the casing of household appliances, electrical appliances, industrial machines and new energy materials.

[0019] Beneficial effects of the present invention:

[0020] 1. The present invention realizes efficient flame retardancy of PC materials by compounding organic phosphorus flame retardants and inorganic flame retardants, while avoiding the negative impact of a single flame retardant on the performance of PC materials;

[0021] 2. The present invention adopts a compound system of hindered phenol antioxidants and phosphite antioxidants as antioxidants, which effectively improves the antioxidant properties of PC materials, thereby enhancing their wet heat aging properties;

[0022] 3. The present invention utilizes maleic anhydride grafted polymer as a compatibilizer to improve the compatibility of flame retardants, antioxidants and PC resins, and improve the uniformity and stability of PC materials;

[0023] 4. The present invention adds glass fiber to PC material by melt blending, which significantly improves the mechanical properties and thermal stability of PC material. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] Example 1

[0026] A method for preparing a highly flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging, the method comprising the following steps:

[0027] S1, 85 parts of PC resin, 2 parts of organophosphorus flame retardant, 3 parts of inorganic flame retardant, 0.2 parts of hindered phenol antioxidant, 0.2 parts of phosphite antioxidant, 0.5 parts of maleic anhydride grafted polymer and 0.1 parts of silane coupling agent are mixed uniformly to obtain a premix;

[0028] S2, melt-blending the premix with 10 parts of glass fiber to obtain a melt blend, the melting temperature is 260-280° C., and the melting time is 5-10 minutes;

[0029] S3, melting and granulating the molten blend to obtain a flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging.

[0030] Example 2

[0031] A method for preparing a highly flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging, the method comprising the following steps:

[0032] S1, 72 parts of PC resin, 3 parts of organophosphorus flame retardant, 5 parts of inorganic flame retardant, 0.2 parts of hindered phenol antioxidant, 0.2 parts of phosphite antioxidant, 3 parts of maleic anhydride grafted polymer and 0.5 parts of silane coupling agent are mixed uniformly to obtain a premix;

[0033] S2, melt-blending the premix with 15 parts of glass fiber to obtain a melt blend, the melting temperature is 270-290° C., and the melting time is 8-12 minutes;

[0034] S3, melting and granulating the molten blend to obtain a flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging.

[0035] Example 3

[0036] A method for preparing a highly flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging, the method comprising the following steps:

[0037] S1, 61.5 parts of PC resin, 2.5 parts of organophosphorus flame retardant, 2.5 parts of inorganic flame retardant, 0.2 parts of hindered phenol antioxidant, 0.2 parts of phosphite antioxidant, 2 parts of maleic anhydride grafted polymer and 1.5 parts of silane coupling agent are mixed uniformly to obtain a premix;

[0038] S2, then melt-blending the premix with 20 parts of glass fiber to obtain a melt blend, the melting temperature is 250-270° C., and the melting time is 10-15 minutes;

[0039] S3, melting and granulating the molten blend to obtain a flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging.

[0040] Comparative Example 1

[0041] Compared with Example 1, in Comparative Example 1, 5 parts of organophosphorus flame retardant are added in step S1, and no inorganic flame retardant is added. Other components and preparation steps are the same as those in Example 1.

[0042] Comparative Example 2

[0043] Compared with Example 1, in Comparative Example 2, 5 parts of inorganic flame retardant are added in step S1, and no organophosphorus flame retardant is added. Other components and preparation steps are the same as those in Example 1.

[0044] Comparative Example 3

[0045] Compared with Example 1, in Comparative Example 3, 0.4 parts of hindered phenol antioxidants were added in step S1, and no phosphite antioxidants were added. Other components and preparation steps were the same as those in Example 1.

[0046] Comparative Example 4

[0047] Compared with Example 1, in Comparative Example 4, 0.4 parts of phosphite antioxidants were added in step S1, and no hindered phenol antioxidants were added. Other components and preparation steps were the same as those in Example 1.

[0048] Comparative Example 5

[0049] Compared with Example 1, the compatibilizer added in step S1 is a common compatibilizer, and the other components and preparation steps are the same as those in Example 1.

[0050] Performance Test:

[0051] The performance tests were conducted on Comparative Examples 1 to 5 and Examples 1 to 3 as well as the prepared moisture-heat aging resistant flame-retardant glass fiber reinforced PC materials. The specific test standards and test results are shown in Tables 1 to 4.

[0052] Table 1 Performance test results of comparative examples 1 to 5

[0053] performance Test Standards Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Tensile Strength GB / T1040 61.3 58.9 60.8 60.1 60.4 Elongation at break GB / T1040 15.1 14.5 13.3 13.1 13.5 Bending Strength GB / T9341 105.6 98.5 98.0 97.2 96.9 Flexural modulus GB / T9341 3587 3432 3596 3421 3332 Izod notched impact GB / T1843 8.2 12.4 11.9 12.8 13.1 Flame retardant UL94 V-0 V-1 V-0 V-0 V-0

[0054] Table 2 Performance test results of Examples 1 to 3

[0055] performance Test Standards Example 1 Example 2 Example 3 Tensile Strength GB / T1040 59.6 89.8 109.6 Elongation at break GB / T1040 13.4 4.6 3.5 Bending Strength GB / T9341 96.1 142.0 186 Flexural modulus GB / T9341 3330 5609 7808 Izod notched impact GB / T1843 12.9 11.3 11.5 Flame retardant UL94 V-0 V-0 V-0

[0056] Table 3 Performance of Examples 1 to 3 after D85 aging for 1000h (D85 test conditions: temperature 85°C, humidity 85% RH)

[0057]

[0058]

[0059] Table 4 Comparative Examples 1 to 5 D85 performance after aging for 1000h (D85 test conditions: temperature 85°C, humidity 85% RH)

[0060]

[0061] By comparing Example 1 with Comparative Examples 1 and 2, it can be found that if only organic phosphorus flame retardants are used, although a higher flame retardant grade can be achieved, the wet heat aging resistance is poor and the impact retention rate is low; if only inorganic flame retardants are used, although the material has good wet heat aging resistance, the flame retardant is unstable and it is difficult to meet the use requirements; through Comparative Examples 3-4, it can be found that hindered phenol antioxidants have little effect on the wet heat aging performance of the material, while phosphate antioxidants have a greater effect on the wet heat aging performance; through Comparative Example 5, it can be found that the type of compatibilizer has little effect on the wet heat aging performance of the material. By performing performance tests on the wet heat aging resistant high flame retardant glass fiber reinforced PC material prepared in Examples 1-3, it is found that the material has good flame retardant properties and wet heat aging performance, while maintaining excellent mechanical properties and processing properties. Specifically, the material achieved a high flame retardant level in the flame retardant test, meeting high safety requirements; in the wet heat aging test, the material's performance changed little, showing good resistance to wet heat aging; in addition, the material's mechanical properties and processing performance have also been significantly improved, meeting the needs of practical applications.

[0062] The present invention successfully prepares a highly flame-retardant glass fiber reinforced PC material with resistance to damp heat aging through reasonable formula design and preparation process. The material further improves its flame retardant performance and damp heat aging performance on the basis of maintaining the original excellent performance of PC, and has broad application prospects. At the same time, the preparation method of the present invention is simple and easy to implement, can be mass-produced, and is expected to make important contributions to the development of the field of polymer materials.

[0063] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0064] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging. It is characterized in that The raw materials for preparing the PC material include the following components by weight: 70-80 parts of polycarbonate resin, 10-20 parts of glass fiber, 5-10 parts of flame retardant, 5-10 parts of toughening agent, 0.1-0.5 parts of antioxidant, 0.4-1 parts of lubricant, 0.3-0.8 parts of anti-dripping agent, 0.1-1 parts of light stabilizer and 0.1-1 parts of anti-ultraviolet agent; The flame retardant is a composite system of a phosphorus-containing compound and an inorganic flame retardant, and the mass ratio of the phosphorus-containing compound to the inorganic flame retardant is (1-3):(2-4); the phosphorus-containing compound is selected from at least one of hexaphenoxycyclotriphosphazene, triphenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl phosphate)], and triphenylphosphine oxide, and the inorganic flame retardant is selected from at least one of potassium perfluorobutyl sulfonate, potassium benzenesulfonylbenzenesulfonate, sodium p-toluenesulfonate, and sodium trichlorophenyl sulfonate; The antioxidant is a compound system of a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (1-2):

1.

2. The heat-wet aging-resistant flame-retardant glass fiber reinforced PC material according to claim 1, It is characterized in that The polycarbonate is at least one of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate and organosilicon-modified polycarbonate; the density of the polycarbonate is 1.19-1.21 g / cm 3 , melt index is 7-22g / 10min.

3. The heat-wet aging-resistant flame-retardant glass fiber reinforced PC material according to claim 1, It is characterized in that The toughening agent is at least one of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, acrylic ester copolymer, acrylonitrile-styrene-acrylate copolymer and silicone rubber graft copolymer.

4. The heat-wet aging-resistant flame-retardant glass fiber reinforced PC material according to claim 1, It is characterized in that The light stabilizer is at least one of salicylates, benzoates, benzophenones, benzotriazoles, substituted acrylonitriles, oxamides, organic nickel complexes and hindered amine ultraviolet absorbers.

5. The heat-wet aging-resistant flame-retardant glass fiber reinforced PC material according to claim 1, It is characterized in that The lubricant is at least one of polyethylene wax, calcium stearate and silicone.

6. The heat-wet aging-resistant flame-retardant glass fiber reinforced PC material according to claim 1, It is characterized in that The anti-dripping agent is at least one of SAN-coated polytetrafluoroethylene and MMA-coated polytetrafluoroethylene.

7. A method for preparing a highly flame-retardant glass fiber reinforced PC material resistant to moisture and heat aging as described in any one of claims 1 to 6, It is characterized in that The preparation method comprises the following steps: S1. Evenly mix PC resin, flame retardant, antioxidant, compatibilizer and coupling agent to obtain a premix; S2, melt-blending the premix and the glass fiber to obtain a melt blend; S3, melting and granulating the molten blend to obtain a flame-retardant glass fiber reinforced PC material that is resistant to moisture and heat aging.

8. Application of the heat-moisture aging-resistant flame-retardant glass fiber reinforced PC material as claimed in any one of claims 1 to 7 in housings of household appliances, electrical appliances, industrial machines and new energy materials.

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