Long-glass-fiber-reinforced flame-retardant polycarbonate material and use thereof

Abstract

The application discloses a long glass fiber reinforced flame-retardant polycarbonate material and application thereof, 50-74 parts of bisphenol A type polycarbonate, 24.7-38.4 parts of continuous glass fiber, 0.1-10 parts of a flame retardant, 0.1-0.3 parts of a dispersing agent, 0.5 parts of an anti-dripping agent, 0.2 parts of an antioxidant, 0.2-0.3 parts of a lubricant, and 0.1-0.3 parts of an anti-glass fiber exposure agent; the retention length of the continuous glass fiber is 3-4 mm, mechanical properties and flame retardancy of the material are considered, the material has low floating fiber and good light transmittance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of engineering plastics, in particular to a long-glass-fiber-reinforced flame-retardant polycarbonate material and application thereof. BACKGROUND

[0002] Polycarbonate (PC) is a highly transparent amorphous thermoplastic and one of the five engineering plastics. The performance of aromatic PC is the best, and the commonly used PC is bisphenol A type PC, which is also the most widely used PC material. Polycarbonate has a unique high light transmittance, high impact resistance, dimensional stability and easy processing, and occupies an extremely important position in the optical field. Due to its excellent comprehensive performance, PC is widely used in building materials, automobiles, medical equipment, optical lighting and packaging fields.

[0003] Long-glass-fiber-reinforced PC material has high strength, high impact resistance and good dimensional stability, and is a "strong and tough" material. After adding glass fiber to PC, the mechanical properties, heat resistance and dimensional stability of PC are greatly improved. In practical applications, it can replace steel and reinforced engineering plastics to meet the use requirements in the fields of light weapon packaging boxes, automobile door panels and home appliance lining plates.

[0004] According to the characteristics of long glass fiber, it is relatively easy to cause fiber floating when used to reinforce polycarbonate. There are few reports on long-glass-fiber-reinforced PC material, and the current public patents are CN 113462141 A and CN 105694410 A, which respectively involve PC composite material with low fiber floating effect and PC&PBT alloy product. Both of them are non-flame-retardant products, while the application scenarios of long-glass-fiber-reinforced products all have flame-retardant requirements. The "wick" effect of long-glass-fiber-reinforced PC products is more serious than that of short-glass-fiber-reinforced products during combustion, and it is difficult to achieve a higher level of flame-retardant effect. At the same time, the flame-retardant stability is poor, so it is a big challenge to introduce flame-retardant performance in the long-glass-fiber-reinforced PC product scheme. At the same time, the introduction of long glass fiber will significantly reduce the light transmittance of the product. SUMMARY

[0005] Therefore, the present application provides a long-glass-fiber-reinforced flame-retardant polycarbonate material and application thereof, which takes into account the mechanical properties and flame retardancy of the material, has low fiber floating and good light transmittance.

[0006] To achieve the above technical purposes, the present application adopts the following technical scheme:

[0007] In a first aspect, the application provides a long glass fiber reinforced flame-retardant polycarbonate material, which comprises the following components in mass fraction: 50-74 parts of bisphenol A polycarbonate, 24.7-38.4 parts of continuous glass fiber, 0.1-10 parts of flame retardant, 0.1-0.3 parts of dispersant, 0.2-1.0 parts of anti-dripping agent, 0.05-0.2 parts of antioxidant, 0.2-1.0 parts of lubricant, and 0.1-1.0 parts of anti-glass fiber exposure agent; the retention length of the continuous glass fiber is 3-4 mm.

[0008] Preferably, the melt mass flow rate of the bisphenol A polycarbonate is 22-60 g / 10 min under the test condition of 300℃ / 1.2 kg.

[0009] Preferably, the continuous glass fiber is one or more of round glass fiber and flat glass fiber.

[0010] Preferably, the diameter of the round glass fiber is 10-15 mm, and the flatness ratio of the flat glass fiber is 3.5-4.5.

[0011] Preferably, the mass percentage of sodium in the continuous glass fiber is 0.1-2%, and the mass percentage of titanium is 0.01-0.1%.

[0012] Preferably, the refractive index of the continuous glass fiber is 1.56-1.59.

[0013] Preferably, the flame retardant is one or more of sulfonate flame retardant and phosphorus-containing flame retardant.

[0014] Preferably, the sulfonate flame retardant includes one or more of potassium perfluoroalkyl sulfonate, benzenesulfonyl potassium, and sodium p-toluenesulfonate; and the phosphorus-containing flame retardant includes one or more of hexaphenoxycyclotriphosphazene, triphenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), and resorcinol bis[diphenyl (2,6-dimethylphenyl phosphate)].

[0015] Preferably, the dispersant includes one or more of maleic anhydride grafted PE / PP and GMA grafted PE / P.

[0016] In the application, the anti-dripping agent is one or both of polytetrafluoroethylene powder and coated polytetrafluoroethylene; the antioxidant is one or both of hindered phenolic antioxidant and phosphorous antioxidant, such as antioxidant 1010, antioxidant 1076, and antioxidant 168; the lubricant is one or more of pentaerythritol stearate, PE wax, and oxidized polyethylene wax OPE; and the anti-glass fiber exposure agent is one or more of branched styrene and acrylate copolymer EMI-150B, stearic acid amide TAF, and oleic acid amide.

[0017] In the second aspect, the application provides an application of the long glass fiber reinforced flame-retardant polycarbonate material in automobile door panels, weapon packaging boxes and home appliance manufacturing.

[0018] In the application, the average length of the continuous glass fiber is 3-4 mm, and the long glass fiber reinforced PC material generally has a higher average length of 3-4 mm of the glass fiber in the reinforced modified PC (the glass fiber reinforcement is generally 100-1000 microns), and the dispersion and orientation of the glass fiber in the PC resin are poor, so that the long glass fiber reinforced PC is very easy to cause the exposure and floating of the glass fiber, and the appearance effect is poor and the light transmission effect is also poor. The long glass fiber reinforced flame-retardant polycarbonate material prepared from the components of the application has the following beneficial effects: the long glass fiber reinforced flame-retardant polycarbonate material of the application takes the long glass fiber and the polycarbonate system as the matrix, and the dispersion and orientation of the long glass fiber in the polycarbonate resin are beneficial to improving the mechanical properties; the combination of the anti-glass fiber exposure agent and the dispersant of the application can overcome the defects of the long glass fiber reinforced system that the glass fiber is easy to be exposed and floating, and finally obtain the long glass fiber reinforced flame-retardant polycarbonate material which has good flame-retardant properties and high rigidity, and can also optimize and improve the appearance effect of the long glass fiber reinforced system and weaken the floating. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the application clearer, the application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the application and not to limit the application.

[0020] The other raw materials in the examples and comparative examples of the application can be obtained by market purchase;

[0021] Bisphenol A polycarbonate-1: aromatic polycarbonate, brand PC 2220, Wanhua Chemical Group Co., Ltd., MFR = 22.

[0022] Bisphenol A polycarbonate-2: aromatic polycarbonate, brand PC 2600, Wanhua Chemical Group Co., Ltd., MFR = 60.

[0023] Bisphenol A polycarbonate-3: aromatic polycarbonate, brand PC 2350, Wanhua Chemical Group Co., Ltd., MFR = 35.

[0024] Bisphenol A polycarbonate-4: aromatic polycarbonate, brand PC LXTY 1609, Luxi Chemical Group Co., Ltd., MFR = 10.

[0025] Aromatic polycarbonate-5: aromatic polycarbonate, brand ASL-80A, Shanghai Osel Material Technology Co., Ltd., MFR = 80.

[0026] Glass fiber: Round glass fiber-1 : Grade 534A, China Jushi Co. Ltd. Na content of 0.20% by mass, alkali-free glass fiber, continuous glass fiber of 3 mm in length and 10 μm in diameter, Ti content of 0.01% by mass, refractive index of 1.56.

[0027] Glass fiber: Round glass fiber-2: Grade 307NB, Chongqing International Composite Material Co. Ltd. Na content of 0.12%, alkali-free glass fiber, continuous glass fiber of 3 mm in length and 15 μm in diameter, Ti content of 0.23%, refractive index of 1.59.

[0028] Glass fiber: Round glass fiber-3: Na content of 0.20% by mass, alkali-free glass fiber, continuous glass fiber of 1 mm in length and 10 μm in diameter, Ti content of 0.01% by mass, refractive index of 1.55.

[0029] Glass fiber: Round glass fiber-4: Na content of 0.20% by mass, alkali-free glass fiber, continuous glass fiber of 3 mm in length and 10 μm in diameter, Ti content of 0.1% by mass, refractive index of 1.58.

[0030] Glass fiber: Round glass fiber-5: Na content of 0.20% by mass, alkali-free glass fiber, continuous glass fiber of 3 mm in length and 10 μm in diameter, Ti content of 0.23% by mass, refractive index of 1.59.

[0031] Glass fiber: Round glass fiber-6: Na content of 0.20% by mass, alkali-free glass fiber, continuous glass fiber of 3 mm in length and 10 μm in diameter, Ti content of 0.05% by mass, refractive index of 1.56.

[0032] Glass fiber: Flat glass fiber-1 : Continuous glass fiber of 4 mm in length and 3.5 in flat ratio, Grade T436, Taishan Glass Fiber Co. Ltd. Na content of 0.12%, alkali-free glass fiber, Ti content of 0.03%, refractive index of 1.56.

[0033] Glass fiber: Flat glass fiber-2: Continuous glass fiber of 4 mm in length and 4.5 in flat ratio, Grade F-534A, China Jushi Co. Ltd. Na content of 0.08%, alkali-free glass fiber, Ti content of 0.13%, refractive index of 1.59.

[0034] Glass fiber: Flat glass fiber-3: Continuous glass fiber of 6 mm in length and 3.5 in flat ratio, Na content of 0.12%, alkali-free glass fiber, Ti content of 0.03%, refractive index of 1.55.

[0035] Glass fiber: Flat glass fiber-4: continuous glass fiber with length of 4mm and flat ratio of 6, Na content of 3%, low alkali glass fiber, Ti content of 0.03%, refractive index of 1.56.

[0036] Glass fiber: Flat glass fiber-5: continuous glass fiber with length of 4mm and flat ratio of 6, Na content of 0.05%, alkali-free glass fiber, Ti content of 0.03%, refractive index of 1.56.

[0037] Glass fiber: Flat glass fiber-6: continuous glass fiber with length of 6mm and flat ratio of 3.5, Na content of 0.12%, alkali-free glass fiber, Ti content of 0.03%, refractive index of 1.56.

[0038] Flame retardant-1: Potassium perfluorobutylsulfonate, FR-2025, purchased from 3M Company.

[0039] Flame retardant-2: Resorcinol bis [di (2, 6-dimethylphenyl phosphate)], WSFR-RDP, purchased from Zhejiang Wansheng Co., Ltd.

[0040] Flame retardant-3: Hexaphenoxycyclotriphosphazene, FP-100, purchased from Jiangsu Yakke Technology Co., Ltd.

[0041] Antioxidant: Hindered phenolic antioxidant, n-octadecyl β-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, commercially available, and the same substance was used in parallel experiments.

[0042] Anti-dripping agent: Coated polytetrafluoroethylene, FD3150, purchased from Shanghai Lujie Polymer Technology Co., Ltd.

[0043] Lubricant: Pentaerythritol tetrastearate, commercially available, and the same substance was used in parallel experiments.

[0044] Dispersant-1: PP grafted maleic anhydride PP-g-MAH, P353, DuPont China Group Co., Ltd.

[0045] Dispersant-2: POE grafted glycidyl methacrylate POE-g-GMA, SOG-02, Jiaiyirong Polymer (Shanghai) Co., Ltd.

[0046] Anti-glass fiber exposure agent: Branched styrene and acrylic ester copolymer, EMI-150B, Jiaiyirong Polymer (Shanghai) Co., Ltd.

[0047] The application is further illustrated by specific examples as follows.

[0048] Examples 1-10

[0049] A long glass fiber reinforced flame-retardant polycarbonate material, raw materials of which include components in mass fractions as shown in Table 1, and a preparation method thereof is provided.

[0050] S1. According to the proportion, the pre-mixture of components except glass fiber is weighed to obtain a pre-mixture;

[0051] S2. The pre-mixture of step S1 is put into an extruder for melt blending and extrusion granulation to obtain a polycarbonate composition.

[0052] The extruder is a double screw extruder, the screw length-diameter ratio of the double screw extruder is 36:1, the barrel temperature of the double screw extruder is 200-260℃, the screw rotation speed of the double screw extruder is 500-800r / min, the side of the double screw porous die is opened at a certain angle to facilitate the continuous glass fiber to be guided into the molten resin matrix from the opening, and the glass fiber is a continuous fiber in the modified PC resin strip before cutting; the material strip is cooled by water cooling, and then cut into long glass fiber reinforced PC particles with a length of 3-6mm by a cutting machine.

[0053] Table 1 Component preparation of examples 1-10

[0054]

[0055]

[0056] Examples 11-16

[0057] Examples 11-16 are the same as example 1 except that the component preparation is shown in Table 2.

[0058] Table 2 Component preparation of examples 11-16

[0059]

[0060]

[0061] Comparative examples 1-11

[0062] Comparative examples 1-11 are the same as example 1 except that the component preparation is shown in Table 3.

[0063] Table 3 Component preparation of comparative examples 1-11

[0064]

[0065]

[0066] Test and evaluation

[0067] The long glass fiber reinforced flame-retardant polycarbonate materials of the above examples and comparative examples were subjected to performance evaluation:

[0068] Gloss: GB / T 8807-1988, tested as standard bars by injection molding;

[0069] Melt index: ISO 1133-2011, the melt index of the granular material was tested by reference standard, the conditions were 300℃ / 1.2kg;

[0070] Flexural modulus: ISO 178-2010, tested as ISO flexural bars by injection molding;

[0071] Flexural strength: ISO 178-2010, tested as ISO flexural bars by injection molding;

[0072] Shrinkage: GB / T 39818-2021, tested as standard bars by injection molding;

[0073] Flame retardant performance: UL-94, tested as ISO burning bars by injection molding;

[0074] Visible light transmittance: ISO 13468-2:1999, tested as standard bars by injection molding;

[0075] Na / Ti content test: ICP-AES spectroscopy was used to determine the element content in the material;

[0076] Refractive index: GB / T 34184-2017 infrared optical glass infrared refractive index test method.

[0077] The results are shown in Tables 4 and 5:

[0078] Table 4 Performance evaluation results of examples

[0079]

[0080] Table 4 Performance evaluation results of examples

[0081]

[0082] Table 5 Performance evaluation results of comparative examples

[0083]

[0084] Compared with Example 1-3 and Comparative Example 6-7, it can be seen that, by adjusting the content of continuous glass fiber, it is shown that: reducing the amount of glass fiber, the modulus of the composite material is reduced to about 4000 MPa, which cannot meet the high modulus application field of long glass fiber reinforced PC; when the amount of glass fiber is more than 40 parts, the mechanical properties of the composite material increase, but the gloss of the composite material decreases sharply, the appearance of the fiber is very serious, and the visible light transmittance decreases very obviously, almost no light transmittance.

[0085] Example 1, Example 4-5, Comparative Example 1-2, by adjusting the type of bisphenol A polycarbonate, it can be seen that: when the flowability of polycarbonate is between 22-60, the long glass fiber reinforced PC material has good gloss, mechanical properties and flame retardant performance, when the flowability is too high, the mechanical properties of the composite material will be significantly attenuated, and the flame retardant performance will also decrease; when the flowability is too low, the PC resin cannot better cover the glass fiber, so that the glass fiber is more exposed, resulting in the gloss of the composite material decreasing and the appearance of the fiber being serious.

[0086] Example 2, Example 6-8 and Comparative Example 3-4, by adjusting the type of continuous glass fiber, it can be seen that: whether it is round glass fiber or flat glass fiber, long glass fiber composite PC material with good appearance can be prepared, but the refractive index of the glass fiber plays a decisive role in the light transmittance of the composite material, replacing the glass fiber with a refractive index of 1.59, the light transmittance of the composite material decreases to a certain extent, but is better than that of the composite material prepared by the glass fiber with a refractive index lower than 1.56.

[0087] Example 9, Example 10, by adjusting the type of flame retardant and the type of dispersant, it can be seen that: replacing the flame retardant has no obvious effect on the flame retardant performance of the composite material, but it will damage the visible light transmittance of the composite material to a certain extent, and replacing the dispersant will obviously reduce the gloss of the composite material, which shows that the preferred dispersant-1 has a certain degree of decisive effect on the good appearance of the composite material.

[0088] Compared with Example 2, the content of the components of the flame retardant is adjusted in Comparative Examples 8-9, which shows that: when the content of the sulfonate flame retardant is less than 0.1 part, the flame retardant performance cannot meet the requirements of V-0 or 5V; and when the content reaches 15 parts, it will significantly catalyze the degradation of PC, and the molecular chain of PC is significantly degraded during the preparation of the composite material, so that the mechanical properties and the flame retardant performance are significantly reduced, and the appearance of the composite material is also significantly deteriorated. Compared with Example 2, the content of the components of the dispersant is adjusted in Comparative Examples 10-11, which shows that when the content of the dispersant is too low or too high, it cannot help the dispersion and orientation of the long glass fiber, and the gloss and light transmittance of the composite material are low, which shows that the fiber is seriously floating, and the flame retardant performance of the composite material is also significantly reduced due to the poor orientation of the glass fiber in the composite material.

[0089] Compared with Example 6 and Example 8, the titanium content of the glass fiber selected in Example 1 is 0.01%, which is lower than that of Example 6 and Example 8, so the light transmittance of Example 1 in the visible light region is obviously better than that of Example 6 and Example 8, which is mainly due to the fact that the high titanium content leads to the reduction of the light transmittance of the glass fiber in the PC composition.

[0090] Compared with Example 1, different titanium content and sodium content of the glass fiber are selected in Examples 11-16, and the high sodium content will cause serious degradation of PC, which will affect the appearance gloss and light transmittance, and the improper selection of titanium content will lead to low light transmittance of the composition, so the gloss and light transmittance of Example 1 are better than those of Examples 11-16.

[0091] Compared with Example 1, the glass fiber in Comparative Example 12 has a retention length of 6mm, which will cause more serious fiber floating of the composition, and the long retention length of the glass fiber will lead to poor orientation of the glass fiber during the injection molding of the composition, and thus the light transmittance of the composition after injection molding is deteriorated, so the gloss and light transmittance of Comparative Example 12 are low; the gloss of Comparative Examples 1 and 4 is adjusted, and the resin flowability of 1 is better than that of 4, so the gloss of 1 is better.

[0092] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A long glass fiber reinforced flame-retardant polycarbonate material, characterized in that, It comprises the following components in parts by weight: 50-74 parts bisphenol A polycarbonate, 24.7-38.4 parts continuous glass fiber, 0.1-10 parts flame retardant, 0.1-0.3 parts dispersant, 0.2-1.0 parts anti-dripping agent, 0.05-0.2 parts antioxidant, 0.2-1.0 parts lubricant, and 0.1-1.0 parts anti-glass fiber exposure agent, wherein the continuous glass fiber has a retention length of 3-4 mm; The melt flow rate of the bisphenol A type polycarbonate is 22-60 g / 10 min, and the melt index test standard is ISO1133-2011, under the conditions of 300℃ / 1.2 kg. The continuous glass fiber contains sodium at a mass percentage of 0.05%, 0.08%, and 0.1-2%, and titanium at a mass percentage of 0.01-0.1%, 0.13%, and 0.23%. The refractive index of the continuous glass fiber is 1.56-1.59, and the test standard is GB / T 34184-2017; The flame retardant is one or more of sulfonate flame retardants and phosphorus-containing flame retardants; The sulfonate flame retardant includes one or more of perfluoroalkyl sulfonate, benzenesulfonylbenzenesulfonyl potassium, and sodium p-toluenesulfonate; the phosphorus-containing flame retardant includes one or more of hexaphenoxane triphosphazene, triphenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), and resorcinol bis[bis(2,6-dimethylphenyl phosphate)]. The dispersant includes one or more of maleic anhydride-grafted PE / PP, GMA-grafted PE / PP, and POE-g-GMA.

2. The long glass fiber reinforced flame-retardant polycarbonate material according to claim 1, characterized in that, The continuous glass fiber is one or more of round glass fiber and flat glass fiber.

3. The long glass fiber reinforced flame-retardant polycarbonate material according to claim 2, characterized in that, The diameter of the circular glass fiber is 10-15mm, and the flat glass fiber has an aspect ratio of 3.5-4.

5.

4. The application of a long glass fiber reinforced flame-retardant polycarbonate material as described in any one of claims 1-3 in automobile door panels, weapon packaging boxes, and home appliance manufacturing.

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