Polycarbonate composite material as well as preparation method and application thereof

Abstract

The invention discloses a polycarbonate composite material as well as a preparation method and application thereof, and relates to the technical field of modified polycarbonate composite materials. The polycarbonate composite material is prepared from the following components in parts by weight: 60 to 90 parts of PC resin, 1 to 8 parts of titanium dioxide coloring agent, 10 to 40 parts of polysiloxane copolymerized PC resin, 1 to 5 parts of ionic liquid and 0.1 to 1.5 parts of antioxidant, the ionic liquid is composed of positive ions and negative ions, the positive ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions, and the negative ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions. The anions comprise at least one of chloride ions, bromide ions, iodide ions and bis (trifluoromethylsulfonyl) imine ions. Through the special compounding effect of all the components, the white polycarbonate material with good fluidity and excellent hydrolysis resistance is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of modified polycarbonate composites, and in particular to a polycarbonate composite material, a preparation method thereof and an application thereof. Background Art

[0002] Polycarbonate (PC) has excellent comprehensive properties, such as high impact strength, good light transmittance, good dimensional stability, easy coloring, good aging resistance, and excellent electrical insulation properties, etc., and is widely used in the fields of electronics, electrical appliances, construction, machinery, packaging and transportation, etc. However, PC has poor fluidity, large internal stress in the formed products, poor solvent resistance and notch sensitivity, etc. With the development of electronic products, people's requirements for plastic parts are getting higher and higher. For example, mobile phones, tablet computers, and automotive interior shell parts are not only very thin, but also have higher and higher requirements for the retention rate of environmental resistance performance. Therefore, the materials suitable for the above-mentioned parts not only have good fluidity, but also require high retention rate of heat and high humidity strength.

[0003] CN104212146A discloses a hydrolysis-resistant polycarbonate composite material, which adopts 25-75 parts of polycarbonate, 20-65 parts of silicone polycarbonate copolymer, 1-10 parts of methyl methacrylate-butadiene-styrene copolymer, 0.3-1.0 part of antioxidant, and 0.3-1.0 part of lubricant. Using methyl methacrylate-butadiene-styrene copolymer as a hydrolysis-resistant agent improves the hydrolysis resistance of the PC material to a certain extent, but leads to a significant reduction in the fluidity of the PC material.

[0004] Therefore, developing a polycarbonate composite material with good fluidity and hydrolysis resistance has broad market application prospects. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a polycarbonate composite material with good fluidity and hydrolysis resistance, a preparation method thereof and an application thereof.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: a polycarbonate composite material, comprising the following components in parts by weight: 60-90 parts of PC resin, 1-8 parts of titanium dioxide colorant, 10-40 parts of polysiloxane copolymerized PC resin, 1-5 parts of ionic liquid, and 0.1-1.5 parts of antioxidant; the ionic liquid is composed of a cation and an anion, and the cation includes at least one of 1-methylpyridinium ion, 1-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-allyl-1-methylpyrrolidinium, and 1-butyl-1-methylpyrrolidinium, and the anion includes at least one of chloride ion, bromide ion, iodide ion, and bis(trifluoromethylsulfonyl)imide ion.

[0007] Preferably, the weight percentage of the PC resin in the polycarbonate composite material is not less than 50%.

[0008] Preferably, the PC resin is a bisphenol A polycarbonate resin, and the polysiloxane copolymerized PC resin is a polysiloxane copolymerized bisphenol A polycarbonate resin.

[0009] Optionally, the weight portion of the PC resin is one of 60 parts, 61 parts, 63 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts or the range value of any two of them; the titanium dioxide colorant is one of 1 part, 2 parts, 3 parts, 5 parts, 8 parts or the range value of any two of them; the polysiloxane copolymerized PC is one of 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts or the range value of any two of them; the ionic liquid is one of 1 part, 1.1 parts, 1.3 parts, 1.5 parts, 2 parts, 2.1 parts, 2.3 parts, 2.5 parts, 3 parts, 3.1 parts, 3.5 parts, 4 parts, 4.1 parts, 4.3 parts, 4.5 parts, 5 parts or the range value of any two of them; the antioxidant is one of 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.1 part, 1.3 part, 1.5 parts or the range value of any two of them.

[0010] Through the special compounding effect of the titanium dioxide colorant, the polysiloxane copolymerized PC, and the ionic liquid, the present invention together prevents the polyester bond in the PC molecular chain from breaking under high temperature and high humidity, thereby preparing a white polycarbonate material with good fluidity and excellent hydrolysis resistance.

[0011] Preferably, the weight ratio of the titanium dioxide colorant, the polysiloxane copolymerized PC, and the ionic liquid is titanium dioxide colorant: polysiloxane copolymerized PC: ionic liquid = (1 - 2): (5 - 10): 1.

[0012] The inventor found in the actual experiment process that when the weight ratio of the titanium dioxide colorant, the polysiloxane copolymerized PC, and the ionic liquid is within the above specific range, the prepared polycarbonate composite material has better hydrolysis resistance and better fluidity.

[0013] Preferably, the ionic liquid includes at least one of 1-butylpyridinium chloride and 1-butyl-4-methylpyridinium bromide.

[0014] Preferably, the weight-average molecular weight of the polysiloxane copolymerized PC is 15,000 - 28,000. Further preferably, the weight-average molecular weight of the polysiloxane copolymerized PC is 17,000 - 22,000. The weight-average molecular weight of the polysiloxane copolymerized PC is measured by GPC; the melt mass flow rate of the polysiloxane copolymerized PC is 5 - 35 g / 10 min according to ISO 1133-2022 under the conditions of a test temperature of 300 °C and a load of 1.2 kg; based on 100% by mass of the polysiloxane copolymerized PC, the mass percentage of siloxane in the polysiloxane copolymerized PC is 1 - 15%. ， The mass percentage of siloxane in the polysiloxane copolymerized PC is measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0015] Optionally, the weight-average molecular weight of the polysiloxane copolymerized PC is one of 15,000, 17,000, 18,000, 19,000, 20,000, 21,000, 22,000, 25,000, 26,000, 27,000, 28,000 or the range value of any two of them; the melt mass flow rate of the polysiloxane copolymerized PC is one of 35 g / 10 min, 30 g / 10 min, 26 g / 10 min, 18 g / 10 min, 16 g / 10 min, 14 g / 10 min, 12 g / 10 min, 10 g / 10 min, 8 g / 10 min, 6 g / 10 min, 5 g / 10 min or the range value of any two of them according to ISO 1133-2022 under the conditions of a test temperature of 300 °C and a load of 1.2 kg; based on 100% by mass of the polysiloxane copolymerized PC, the mass percentage of silicon element in the polysiloxane copolymerized PC is one of 1%, 2%, 3%, 5%, 8%, 10%, 10%, 13%, 14%, 15% or the range value of any two of them.

[0016] Preferably, the mass percentage of TiO2 in the titanium dioxide colorant is ≥92%. The test method for the mass percentage of TiO2 in the titanium dioxide is the XFR method.

[0017] Optionally, the mass percentage of TiO2 in the titanium dioxide colorant is one of 92%, 93%, 95%, 96%, 97% or the range value of any two of them.

[0018] Preferably, the melt mass flow rate of the PC resin is 1 - 50 g / 10 min according to ISO 1133-2022 under the conditions of a test temperature of 300 °C and a load of 1.2 kg; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

[0019] Preferably, the PC resin has a melt mass flow rate of 1 g / 10 min, 3 g / 10 min, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 18 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 43 g / 10 min, 45 g / 10 min, 50 g / 10 min or a range value of any two of them under the conditions of a test temperature of 300 °C and a load of 1.2 kg according to ISO 1133-2022.

[0020] Further preferably, the hindered phenol antioxidant includes at least one of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and bis[β-(3,5-di-tert-butyl-4-hydroxybenzoyl)] hydrazine; the phosphite antioxidant includes at least one of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphite.

[0021] In addition, the present invention provides a method for preparing the polycarbonate composite material, which includes the following steps: mixing each component evenly, followed by melt extrusion and pelletizing to obtain the polycarbonate composite material.

[0022] Preferably, the conditions for melt extrusion are: 180 ± 10 °C, 230 ± 10 °C, 240 ± 10 °C, 240 ± 10 °C, 240 ± 10 °C, 230 ± 10 °C, and the rotation speed is 200 - 300 rpm.

[0023] Furthermore, the present invention provides the application of the polycarbonate composite material in the preparation of mobile phones, tablet computers, and automotive interior housing parts.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: Through the special compounding effect of titanium dioxide colorant, polysiloxane copolymerized PC, and ionic liquid, assisted by traditional antioxidants, the polyester bonds in the PC molecular chain are prevented from breaking under high temperature and high humidity, thereby preparing a white polycarbonate material with good fluidity and excellent hydrolysis resistance. Detailed Embodiments

[0025] To better illustrate the purpose, technical solution, and advantages of the present invention, the following will further illustrate the present invention with specific examples. The purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all common ordinary reagents and instruments unless otherwise specified.

[0026] The raw materials used in the examples and comparative examples are described as follows, but are not limited to these materials:

[0027] PC Resin - 1: Melt mass flow rate is 3 g / 10 min (300 °C, 1.2 kg), purchased from Samyang Chemical, grade TRIREX 3030PJ;

[0028] PC Resin - 2: Melt mass flow rate is 22 g / 10 min (300 °C, 1.2 kg), purchased from Idemitsu Kosan Co., Ltd., Japan, grade FN 1900;

[0029] PC Resin - 3: Melt mass flow rate is 42 g / 10 min (300 °C, 1.2 kg), purchased from Sabic, grade LEXAN TM Resin HF4010SR;

[0030] Titanium Dioxide Colorant - 1: TiO₂ content is 95%, grade KRONOS2225, KRONOS;

[0031] Titanium Dioxide Colorant - 2: TiO₂ content is 92%, grade PC - 3, ISK Co., Ltd., Japan;

[0032] Titanium Dioxide Colorant - 3: TiO₂ content is 97%, grade R 103, Chemours;

[0033] Polysiloxane Copolycarbonate - 1: Melt mass flow rate is 32 g / 10 min (300 °C, 1.2 kg), weight - average molecular weight 17000, silicon content 6%, purchased from Idemitsu Kosan Co., Ltd., Japan, grade FG 1700;

[0034] Polysiloxane Copolycarbonate - 2: Melt mass flow rate is 10 g / 10 min (300 °C, 1.2 kg), weight - average molecular weight 22000, silicon content is 4%, purchased from Sabic, grade LEXAN EXL1414T;

[0035] Polysiloxane Copolycarbonate - 3: Melt mass flow rate is 18 g / 10 min (300 °C, 1.2 kg), weight - average molecular weight 19500, silicon content 5%, purchased from Sabic, grade LEXAN TM COPOLYMER EXL9111;

[0036] Polysiloxane Copolycarbonate - 4: Melt mass flow rate is 5 g / 10 min (300 °C, 1.2 kg), weight - average molecular weight 28000, silicon content 5%, purchased from Sabic, grade Lexan EXL1033C;

[0037] Ionic liquid - 1: Purity 97%, 1 - butylpyridinium chloride (CAS: 1124 - 64 - 7), purchased from TCI (Tokyo Chemical Industry) Chemical Company; Anion: chloride ion, Cation: 1 - butylpyridinium ion;

[0038] Ionic liquid - 2: Purity 96%, 1 - butyl - 4 - methylpyridinium bromide (CAS: 65350 - 59 - 6), purchased from TCI Chemical Company; Anion: bromide ion, Cation: 1 - butyl - 4 - methylpyridinium ion;

[0039] Ionic liquid - 3: Purity 97%, 1 - methylpyridinium bis(trifluoromethanesulfonyl)imide (CAS: 742086 - 10 - 8), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - methylpyridinium ion;

[0040] Ionic liquid - 4: Purity 97%, 1 - butyl - 1 - methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (CAS: 223437 - 11 - 4), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - butyl - 1 - methylpyrrolidinium ion;

[0041] Ionic liquid - 5: Purity 96%, tetrabutylphosphonium tetrafluoroborate (CAS: 1813 - 60 - 1), manufacturer TCI Chemical Company; Anion: tetrafluoroborate ion, Cation: tetrabutylphosphonium ion;

[0042] Ionic liquid - 6: Purity 97%, trihexyl(tetradecyl)phosphonium dicyanamide (CAS: 701921 - 71 - 3), manufacturer TCI Chemical Company; Anion: dicyanamide ion, Cation: trihexyl(tetradecyl)phosphonium ion;

[0043] Ionic liquid - 7: Purity 96%, triethylsulfonium bis(trifluoromethanesulfonyl) - imide salt (CAS: 321746 - 49 - 0), TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl) - imide ion, Cation: triethylsulfonium ion;

[0044] The antioxidant is a composite of commercially available hindered phenolic antioxidant 1010 and commercially available phosphite antioxidant PEP - 36 in a mass ratio of 1:5.

[0045] Examples 1 - 16 and Comparative Examples 1 - 4

[0046] Examples of the polycarbonate composite material described in the present invention, the composition components of the polycarbonate composite material are shown in Table 1 and Table 2. The preparation method of the polycarbonate composite material includes the following steps:

[0047] Mix the components evenly, followed by melt extrusion and pelletization to obtain the polycarbonate composite material. The conditions for the melt extrusion are: 180°C, 230°C, 240°C, 240°C, 240°C, 230°C, and the rotation speed is 250 rpm.

[0048] Comparative Examples 1-4

[0049] The differences between each comparative example and the example lie only in the types and ratios of the components, as shown in Table 3.

[0050] Table 1

[0051]

[0052]

[0053] Table 2

[0054] Project Example 12 Example 13 Example 14 Example 15 Example 16 PC Resin-1 75 75 75 60 85 Titanium Dioxide Colorant-1 2 8 5 1 2 Polysiloxane Copolymerized PC-1 20 12 18 36 12 Ionic Liquid-1 2 4 1 3 1 Antioxidant 0.6 0.6 0.6 0.6 0.6

[0055] Table 3

[0056] Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PC Resin-1 75 75 75 75 Titanium Dioxide Colorant-1 6 6 6 6 Polysiloxane Copolymerized PC-1 15 15 15 / Ionic Liquid-1 / / / 3 Ionic Liquid-5 3 / / / Ionic Liquid-6 / 3 / / Ionic Liquid-7 / / 3 / Antioxidant 0.6 0.6 0.6 0.6

[0057] Performance Testing

[0058] To verify the performance of the polycarbonate composite material of the present invention, the products prepared in each example and comparative example are subjected to the following performance tests, and the specific steps are as follows:

[0059] Respectively dry the polycarbonate composite materials provided in the above examples and comparative examples in an oven at 120°C for 3-4 hours, and then injection mold dumbbell-shaped tensile standard specimens of ISO 527-2 1A-2012. The injection molding temperature is 250°C; after placing the injection-molded standard specimens at 25°C and 50% relative humidity for 24 hours, test the performance.

[0060] (1) Tensile strength test before hydrolysis: Injection mold each product into dumbbell-shaped tensile standard specimens according to the ISO 527-2 1A-2012 standard method, and the speed of the tensile test is 50 mm / min;

[0061] Hydrolysis resistance: Injection mold dumbbell-shaped tensile standard specimens of each product, immerse them in hot water at 80 ± 2°C for 500 h, and then adjust them at room temperature for 24 hours and test the tensile strength. The tensile strength is measured in the same manner as in (1). The retention rate of tensile strength after hydrolysis % = tensile strength after hydrolysis ÷ tensile strength before hydrolysis × 100%. The higher the retention rate of tensile strength after hydrolysis, the stronger the hydrolysis resistance.

[0062] (2) Melt flow rate MFR: Test the dried particles according to ISO1133, and the conditions are 300°C and 1.2 kg;

[0063] Hydrolysis resistance: Immerse 100 g of particles in hot water at 80 ± 2 °C for 500 h, then dry at 120 °C for 4 h and test the MFR after hydrolysis. The retention rate of MFR performance after hydrolysis (%) = MFR after hydrolysis ÷ MFR before hydrolysis. The lower the retention rate of MFR after hydrolysis, the more stable the molecular chain of the material and the stronger the hydrolysis resistance of the material.

[0064] The test results are shown in Table 4.

[0065] Table 4

[0066]

[0067]

[0068] As can be seen from the above table, the tensile strength of the polycarbonate composite material prepared in the examples of the present invention can reach more than 55 MPa, the retention rate of tensile strength after hydrolysis of the polycarbonate composite material is more than 70%, and the retention rate of MFR performance after hydrolysis is more than 60%.

[0069] From the comparison of Example 1, Examples 6-8, it can be seen that when the weight-average molecular weight of the polysiloxane copolymerized PC is 17,000-22,000, the prepared polycarbonate composite material has better hydrolysis resistance and better fluidity.

[0070] From the comparison of Example 1, Examples 9-11, Comparative Examples 1-3, it can be seen that the selection of ionic liquid has a great influence on the retention rate of tensile strength after hydrolysis and the retention rate of MFR performance after hydrolysis of the polycarbonate composite material. When the ionic liquid includes at least one of 1-butylpyridinium chloride and 1-butyl-4-methylpyridinium bromide, the retention rate of tensile strength after hydrolysis and the retention rate of MFR performance after hydrolysis of the polycarbonate composite material are higher.

[0071] From the comparison of Example 1, Examples 12-16, Comparative Example 4, it can be seen that through the special compounding effect of titanium dioxide colorant, polysiloxane copolymerized PC and ionic liquid, the present invention prevents the polyester bond in the PC molecular chain from breaking under high temperature and high humidity together. When the weight ratio of titanium dioxide colorant, polysiloxane copolymerized PC and ionic liquid = (1-2):(5-10):1, the prepared polycarbonate composite material has better hydrolysis resistance and better fluidity. Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polycarbonate composite material, characterized in that, It comprises the following components in parts by weight: 60 - 90 parts of PC resin, 1 - 8 parts of titanium dioxide colorant, 10 - 40 parts of polysiloxane copolymerized PC resin, 1 - 5 parts of ionic liquid, and 0.1 - 1.5 parts of antioxidant; the ionic liquid is composed of a cation and an anion, the cation includes at least one of 1 - methylpyridinium ion, 1 - butylpyridinium ion, 1 - butyl - 4 - methylpyridinium ion, 1 - allyl - 1 - methylpyrrolidinium ion, 1 - butyl - 1 - methylpyrrolidinium ion, and the anion includes at least one of chloride ion, bromide ion, iodide ion, bis(trifluoromethanesulfonyl)imide ion.

2. The polycarbonate composite material according to claim 1, characterized in that, The weight ratio of the titanium dioxide colorant, polysiloxane copolymerized PC, and ionic liquid is titanium dioxide colorant:polysiloxane copolymerized PC:ionic liquid = (1 - 2):(5 - 10):

1.

3. The polycarbonate composite material according to claim 1, wherein The ionic liquid includes at least one of 1 - butylpyridinium chloride salt and 1 - butyl - 4 - methylpyridinium bromide salt.

4. The polycarbonate composite material according to claim 1, characterized in that, The weight - average molecular weight of the polysiloxane copolymerized PC is 15000 - 28000, and the melt mass - flow rate of the polysiloxane copolymerized PC is 5 - 35 g / 10 min according to ISO 1133 - 2022 under the conditions of a test temperature of 300 °C and a load of 1.2 kg.

5. The polycarbonate composite material according to claim 1, characterized in that, The mass percentage content of TiO₂ in the titanium dioxide colorant is ≥92%.

6. The polycarbonate composite material according to claim 1, wherein The melt mass - flow rate of the PC resin is 1 - 50 g / 10 min according to ISO 1133 - 2022 under the conditions of a test temperature of 300 °C and a load of 1.2 kg; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

7. The preparation method of the polycarbonate composite material according to any one of claims 1-6, characterized in that, It includes the following steps: mixing the components evenly, followed by melt - extrusion and pelletization to obtain the polycarbonate composite material.

8. The application of the polycarbonate composite material according to any one of claims 1 - 6 in the preparation of mobile phones, tablet computers, and automotive interior housing parts.

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