Halogen-free flame-retardant PC composite material resistant to high temperature, high humidity and aging

Abstract

The invention relates to a high-temperature-resistant, high-humidity-aging-resistant, halogen-free and flame-retardant PC (polycarbonate) composite material which comprises the following components in parts by weight: 50-98.5 parts by mass of polycarbonate; 1-10 parts by mass of a toughening agent; 0.2 to 10 parts by mass of a toughening compatilizer; 0.2 to 10 parts by mass of a flame retardant; 0.05 to 2 parts by mass of an anti-dripping agent; the PC composite material has the beneficial effects that by utilizing the characteristic that the fluidity of the assistant resin material is better than that of PC, the enrichment and wrapping effects on the surface of a product can be realized during injection molding, so that a shielding effect on water and moisture is formed, and the high-temperature and high-humidity resistance of the PC composite material can be remarkably improved; and the flame retardants used in the invention are halogen-free flame retardants, have the characteristics of small addition amount and remarkable flame retardant effect, and can realize and meet the flame retardant requirement and fireproof grade under the condition of ultrathin thickness (less than or equal to 1.0 mm).

Description

[Technical field]

[0001] The invention relates to the technical field of polycarbonate composite materials, in particular to a halogen-free flame-retardant PC composite material which is resistant to high temperature and high humidity aging. [Background technology]

[0002] Polycarbonate (PC, also known as PC resin) is an engineering plastic with excellent comprehensive properties (such as mechanical properties, dimensional stability, toughness, heat resistance, UV resistance and electrical properties). The flame retardant performance and grade of PC itself is UL94V-2, and the three major application areas of its engineering plastics are glass assembly industry, automobile industry and electronics and electrical industry. In actual production and application, according to different needs, such as to enhance toughness, improve molding processing performance, reduce residual deformation, and improve flame retardancy, PC needs to be modified.

[0003] PC's own inability to withstand high temperature and high humidity, aging, hydrolysis, and flame retardancy limits its use in harsh environments. For example, in new energy batteries, equipment, and instruments, there are certain requirements for the material's resistance to high temperature and humidity, as well as its halogen-free flame retardancy. However, the current performance of PC itself cannot meet these requirements.

[0004] In view of this, it is necessary to provide a halogen-free flame-retardant PC composite material that is resistant to high temperature and high humidity aging to solve the above problems. [Summary of the invention]

[0005] The technical problem to be solved by the present invention is that PC itself is not resistant to high temperature and high humidity aging and hydrolysis and has flame retardant properties, which limits its use in harsh environments. For example, in new energy batteries, equipment and instruments, there are certain requirements for the material's high temperature and high humidity resistance and halogen-free flame retardant properties, but the current performance of PC itself cannot meet these requirements. Therefore, the present invention provides a halogen-free flame retardant PC composite material that is resistant to high temperature and high humidity aging to solve the above problems.

[0006] The solution of the present invention to solve the technical problem is:

[0007] A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging, characterized in that it comprises the following components in parts by weight:

[0008] Polycarbonate, 50 to 98.5 parts by mass;

[0009] Toughening agent, 1 to 10 parts by weight;

[0010] Toughening compatibilizer, 0.2 to 10 parts by weight;

[0011] Flame retardant, 0.2 to 10 parts by mass;

[0012] Anti-dripping agent, 0.05 to 2 parts by mass;

[0013] Antioxidant, 0.05 to 2 parts by mass.

[0014] The PC composite material resistant to high temperature and high humidity aging in the present invention refers to a material whose impact resistance can be maintained at 50% or more after a high temperature and high humidity test (temperature 80° C., humidity 85%, time 1000 hours).

[0015] The selected polycarbonate is a compound and use of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of PC is between (5 and 40) g / 10min (300°C / 1.2kg), the weight average molecular weight is between 20,000 and 50,000, and the molecular weight distribution is between 1 and 2.5.

[0016] The toughening agent selected can be a compound of one or more of unsaturated rubber, saturated rubber, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer, polyamide thermoplastic elastomer, high rubber powder, acrylic copolymer (ACR), etc. and their derivatives.

[0017] The selected toughening compatibility agent material can be a compound and use of one or more of carboxylic acid type, cyclic anhydride type (MAH), epoxy type, oxazoline type, imide type, isocyanate type and low molecular type, etc. and their derivatives.

[0018] The flame retardant selected can be a combination of one or more of hypophosphite flame retardants, phosphate flame retardants, sulfonate flame retardants, silicone flame retardants, etc. and their derivatives.

[0019] The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

[0020] The antioxidant selected can be a combination of one or more of hindered phenols, phosphites, thio antioxidants, etc.

[0021] A product, characterized in that the product uses auxiliary resin materials and adds a small amount of halogen-free flame retardant to prepare a halogen-free flame retardant PC composite material that is resistant to high temperature and high humidity aging.

[0022] The beneficial effect of the present invention is that the present invention utilizes the characteristic that the auxiliary resin material has better fluidity than PC, so that the enrichment and wrapping effect on the product surface can be achieved during injection molding, thereby forming a shielding effect on water and moisture, which can significantly improve the high temperature and high humidity resistance of the PC composite material. In addition, the flame retardants used in the present invention are all halogen-free flame retardants, which are environmentally friendly, meet and comply with national and international management and regulations, and will not cause secondary pollution to the environment. In addition, it has the characteristics of small addition amount and significant flame retardant effect, and can achieve and meet the flame retardant requirements and fire protection levels under ultra-thin thickness (≤1.0mm). [Specific implementation method]

[0023] In order to further illustrate the technical means and effects adopted by the present invention, the embodiments of the present invention are described in detail below.

[0024] The present invention provides a high temperature and high humidity aging resistant halogen-free flame retardant PC composite material, which is characterized in that it comprises the following components in parts by mass:

[0025] Polycarbonate, 50 to 98.5 parts by mass;

[0026] Toughening agent, 1 to 10 parts by weight;

[0027] Toughening compatibilizer, 0.2 to 10 parts by weight;

[0028] Flame retardant, 0.2 to 10 parts by mass;

[0029] Anti-dripping agent, 0.05 to 2 parts by mass;

[0030] Antioxidant, 0.05 to 2 parts by mass.

[0031] The PC composite material resistant to high temperature and high humidity aging in the present invention refers to a material whose impact resistance can be maintained at 50% or more after a high temperature and high humidity test (temperature 80° C., humidity 85%, time 1000 hours).

[0032] The selected polycarbonate is a compound and use of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of PC is between (5 and 40) g / 10min (300°C / 1.2kg), the weight average molecular weight is between 20,000 and 50,000, and the molecular weight distribution is between 1 and 2.5.

[0033] The toughening agent selected can be unsaturated rubber (such as nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR)), saturated rubber (such as butyl rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), halogenated butyl rubber), styrene thermoplastic elastomer (such as methyl methacrylate-butadiene-styrene terpolymer (MBS), styrene-butadiene-styrene copolymer (SBS), hydrogenated SBS (SEBS), styrene-isoprene-styrene (SIS)), polyurethane thermoplastic elastomer (such as TPU), polyolefin thermoplastic elastomer (such as chlorinated polyethylene (CPE), ethylene-octene copolymer (POE), thermoplastic dynamic vulcanizate (TPV), ethylene-vinyl acetate copolymer (EVA)), polyamide thermoplastic elastomer (such as TPAE), high rubber powder, acrylic copolymer (ACR), etc. and their derivatives. One or more of the compounding and use.

[0034] The toughening compatibility material selected can be a carboxylic acid type (e.g., ethylene-methyl acrylate copolymer (E-MA)), a cyclic anhydride type (MAH) (e.g., p(St-MMA-MAH), styrene-butadiene-styrene copolymer grafted with maleic anhydride (SBS-g-MAH), styrene-ethylene-butyl copolymer grafted with maleic anhydride (SEBS-g-MAH)), an epoxy type (e.g., glycidyl methacrylate (GMA), ethylene-methyl acrylate-glycidyl methacrylate triblock The compounding and use of one or more of copolymers (E-MA-GMA), p(St-An-GMA)), oxazoline type (e.g., oxazoline grafted PS, i.e., RPS), imide type (e.g., imide modified polyacrylate), isocyanate type (e.g., m-isopropenyl-2,2-dimethylbenzoyl isocyanate) and low molecular type (e.g., reactive compatibilizers, reactive monomers, low molecular weight polymers), etc. and their derivatives, the toughening compatibilizer material is used as an auxiliary resin material in this embodiment.

[0035] The flame retardant selected can be a phosphite flame retardant (such as vinyl aluminum hypophosphite flame retardant, vinyl hypophosphite), a phosphate flame retardant (such as 1,3-phenylene phosphite (2,6-methylphenyl) tetraphosphate, tetraphenyl bisphenol A diphosphate and its derivative flame retardant (BDP), tetraphenyl resorcinol diphosphate and its derivative (RDP) flame retardant, triphenyl phosphate (TPP) flame retardant), a sulfonate flame retardant (such as potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB)), an organosilicon flame retardant (such as polysilborane and its derivative flame retardant, cross-linked polydimethylsiloxane (PDMS)), etc. and their derivatives. One or more of the compounding and use.

[0036] The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

[0037] The antioxidant selected can be a combination of one or more of hindered phenols (such as (β-3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl acrylate), phosphites (such as tris(2,4-di-tert-butylphenyl) phosphite, dioctadecyl alcohol pentaerythritol diphosphite), thio antioxidants, etc.

[0038] Example 1

[0039] A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging comprises the following components in parts by mass: 93.8 parts of polycarbonate, 4 parts of a toughening agent, 0.5 parts of a toughening compatibilizer, 0.5 parts of a sulfonate flame retardant, 0.5 parts of a silicone flame retardant, 0.4 parts of an anti-dripping agent, and 0.3 parts of an antioxidant.

[0040] The polycarbonate used is bisphenol A linear polycarbonate, which is synthesized by phosgene method, with MI=20g / 10min (300°C / 1.2kg), weight average molecular weight between 49000 and 50000, and molecular weight distribution between 1.5 and 2.0.

[0041] Among them, the toughening agent selected is styrene-based thermoplastic elastomer MBS, which can significantly improve the impact resistance of resins and engineering plastics, and at the same time has excellent heat aging resistance and hydrolysis resistance.

[0042] Among them, the toughening compatibilizer material selected is ethylene-methyl acrylate-glycidyl methacrylate triblock copolymer (E-MA-GMA), in which the percentage of methyl acrylate is 15-30%. Its use as an auxiliary material can not only improve the compatibility between PC and the toughening agent, but also significantly improve the high temperature and high humidity resistance of PC composite materials.

[0043] Among them, the compound of sulfonate flame retardant and silicone flame retardant is selected, which has the advantages of small addition amount and can achieve flame retardant requirements and fire protection level in ultra-thin thickness (≤1.0mm).

[0044] Among them, the anti-drip agent selected is non-coated PTFE (pure powder type), which has the characteristics of small addition amount and significant anti-drip effect.

[0045] Among them, the antioxidant selected is a compound of hindered phenols and phosphites, which has a significant synergistic effect and has the characteristics of small addition amount and significant antioxidant and anti-yellowing effects.

[0046] The processing machine used is a twin-screw extruder, and the processing temperature is 270-280°C.

[0047] When preparing the high temperature and high humidity aging resistant halogen-free flame-retardant PC composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded to form granules.

[0048] Example 2

[0049] A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging comprises the following components in parts by mass: 93.3 parts of polycarbonate, 4 parts of a toughening agent, 1 part of a toughening compatibilizer, 0.5 parts of a sulfonate flame retardant, 0.5 parts of a silicone flame retardant, 0.4 parts of an anti-dripping agent, and 0.3 parts of an antioxidant.

[0050] The polycarbonate used is bisphenol A linear polycarbonate, which is synthesized by phosgene method, with MI=20g / 10min (300°C / 1.2kg), weight average molecular weight between 49000 and 50000, and molecular weight distribution between 1.5 and 2.0.

[0051] Among them, the toughening agent selected is styrene-based thermoplastic elastomer MBS, which can significantly improve the impact resistance of resins and engineering plastics, and at the same time has excellent heat aging resistance and hydrolysis resistance.

[0052] Among them, the toughening compatibilizer material selected is ethylene-methyl acrylate-glycidyl methacrylate triblock copolymer (E-MA-GMA), in which the percentage of methyl acrylate is 15-30%. Its use as an auxiliary material can not only improve the compatibility between PC and the toughening agent, but also significantly improve the high temperature and high humidity resistance of PC composite materials.

[0053] Among them, the compound of sulfonate flame retardant and silicone flame retardant is selected, which has the advantages of small addition amount and can achieve flame retardant requirements and fire protection level in ultra-thin thickness (≤1.0mm).

[0054] Among them, the anti-drip agent selected is non-coated PTFE (pure powder type), which has the characteristics of small addition amount and significant anti-drip effect.

[0055] Among them, the antioxidant selected is a compound of hindered phenols and phosphites, which has a significant synergistic effect and has the characteristics of small addition amount and significant antioxidant and anti-yellowing effects.

[0056] The processing machine used is a twin-screw extruder, and the processing temperature is 270-280°C.

[0057] When preparing the high temperature and high humidity aging resistant halogen-free flame-retardant PC composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded to form granules.

[0058] Example 3

[0059] A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging comprises the following components in parts by mass: 92.3 parts of polycarbonate, 4 parts of a toughening agent, 2 parts of a toughening compatibilizer, 0.5 parts of a sulfonate flame retardant, 0.5 parts of a silicone flame retardant, 0.4 parts of an anti-dripping agent, and 0.3 parts of an antioxidant.

[0060] The polycarbonate used is bisphenol A linear polycarbonate, which is synthesized by phosgene method, with MI=20g / 10min (300°C / 1.2kg), weight average molecular weight between 49000 and 50000, and molecular weight distribution between 1.5 and 2.0.

[0061] Among them, the toughening agent selected is styrene-based thermoplastic elastomer MBS, which can significantly improve the impact resistance of resins and engineering plastics, and at the same time has excellent heat aging resistance and hydrolysis resistance.

[0062] Among them, the toughening compatibilizer material selected is ethylene-methyl acrylate-glycidyl methacrylate triblock copolymer (E-MA-GMA), in which the percentage of methyl acrylate is 15-30%. Its use as an auxiliary material can not only improve the compatibility between PC and the toughening agent, but also significantly improve the high temperature and high humidity resistance of PC composite materials.

[0063] Among them, the compound of sulfonate flame retardant and silicone flame retardant is selected, which has the advantages of small addition amount and can achieve flame retardant requirements and fire protection level in ultra-thin thickness (≤1.0mm).

[0064] Among them, the anti-drip agent selected is non-coated PTFE (pure powder type), which has the characteristics of small addition amount and significant anti-drip effect.

[0065] Among them, the antioxidant selected is a compound of hindered phenols and phosphites, which has a significant synergistic effect and has the characteristics of small addition amount and significant antioxidant and anti-yellowing effects.

[0066] The processing machine used is a twin-screw extruder, and the processing temperature is 270-280°C.

[0067] When preparing the high temperature and high humidity aging resistant halogen-free flame-retardant PC composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded to form granules.

[0068] Comparative Example 1

[0069] A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging comprises the following components in parts by mass: 94.3 parts of polycarbonate, 4 parts of a toughening agent, 0 parts of a toughening compatibilizer, 0.5 parts of a sulfonate flame retardant, 0.5 parts of a silicone flame retardant, 0.4 parts of an anti-dripping agent, and 0.3 parts of an antioxidant.

[0070] The polycarbonate used is bisphenol A linear polycarbonate, which is synthesized by phosgene method, with MI=20g / 10min (300°C / 1.2kg), weight average molecular weight between 49000 and 50000, and molecular weight distribution between 1.5 and 2.0.

[0071] Among them, the toughening agent selected is styrene-based thermoplastic elastomer MBS, which can significantly improve the impact resistance of resins and engineering plastics, and at the same time has excellent heat aging resistance and hydrolysis resistance.

[0072] Among them, the compound of sulfonate flame retardant and silicone flame retardant is selected, which has the advantages of small addition amount and can achieve flame retardant requirements and fire protection level in ultra-thin thickness (≤1.0mm).

[0073] Among them, the anti-drip agent selected is non-coated PTFE (pure powder type), which has the characteristics of small addition amount and significant anti-drip effect.

[0074] Among them, the antioxidant selected is a compound of hindered phenols and phosphites, which has a significant synergistic effect and has the characteristics of small addition amount and significant antioxidant and anti-yellowing effects.

[0075] The processing machine used is a twin-screw extruder, and the processing temperature is 270-280°C.

[0076] When preparing the high temperature and high humidity aging resistant halogen-free flame-retardant PC composite material, the components in corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded to form granules.

[0077] After the above embodiments were implemented, they were reproduced according to the same components. After melt extrusion granulation of Embodiment 1, Embodiment 2, Embodiment 3 and Comparative Example 1, the particles in each embodiment were injection molded into standard test specimens on an injection molding machine. The mechanical properties of the obtained materials were tested according to the standards. The test results are shown in Table 1:

[0078] Table 1 Test results

[0079]

[0080] From the test results of Example 1, Example 2, Example 3 and Comparative Example 1, it can be seen that the present invention utilizes auxiliary resin materials and adds a small amount of halogen-free flame retardant to achieve the preparation of a halogen-free flame-retardant PC composite material that is resistant to high temperature and high humidity aging.

[0081] The beneficial effect of the present invention is that the present invention utilizes the characteristic that the auxiliary resin material has better fluidity than PC, so that during injection molding, the enrichment (using corresponding chemical means to collect certain components with smaller content to increase their content in the sample) and wrapping effect on the product surface can be achieved, thereby forming a shielding effect on water and moisture, which can significantly improve the high temperature and high humidity resistance of PC composite materials. In addition, the flame retardants used in the present invention are all halogen-free flame retardants, which are environmentally friendly, meet and comply with national and international management and regulations, and will not cause secondary pollution to the environment. In addition, they have the characteristics of small addition amount and significant flame retardant effect, and can achieve and meet the flame retardant requirements and fire protection levels under ultra-thin thickness (≤1.0mm).

[0082] It should be pointed out that the present invention is not limited to the above-mentioned implementation modes, and any simple modifications, equivalent changes and modifications made to the above-mentioned embodiments by any technician familiar with the profession based on the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A halogen-free flame-retardant PC composite material resistant to high temperature and high humidity aging, characterized in that: The composition comprises the following components in parts by weight: Polycarbonate, 50 to 98.5 parts by mass; Toughening agent, 1 to 10 parts by weight; Toughening compatibilizer, 0.2 to 10 parts by weight; Flame retardant, 0.2 to 10 parts by mass; Anti-dripping agent, 0.05 to 2 parts by mass; Antioxidant, 0.05 to 2 parts by mass.

2. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The selected polycarbonate is a compound and use of one or more of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer PC, cyclohexane bisphenol A polycarbonate, and high-temperature resistant polycarbonate synthesized from bisphenol TMC. The melt mass flow rate MI of PC is between (5 and 40) g / 10min (300°C / 1.2kg), the weight average molecular weight is between 20,000 and 50,000, and the molecular weight distribution is between 1 and 2.

5.

3. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The toughening agent selected can be a compound of one or more of unsaturated rubber, saturated rubber, styrene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyolefin thermoplastic elastomer, polyamide thermoplastic elastomer, high rubber powder, acrylic copolymer (ACR), etc. and their derivatives.

4. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The selected toughening compatibility agent material can be a compound and use of one or more of carboxylic acid type, cyclic anhydride type (MAH), epoxy type, oxazoline type, imide type, isocyanate type and low molecular type, etc. and their derivatives.

5. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The flame retardant selected can be a combination of one or more of hypophosphite flame retardants, phosphate flame retardants, sulfonate flame retardants, silicone flame retardants, etc. and their derivatives.

6. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

7. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The antioxidant selected can be a combination of one or more of hindered phenols, phosphites, thio antioxidants, etc.

8. The high temperature and high humidity aging resistant halogen-free flame retardant PC composite material according to claim 1, characterized in that: The selected processing machine is a twin-screw extruder, and the processing temperature is 270-280°C.

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