Polycarbonate composition as well as preparation method and application thereof

Abstract

The invention discloses a polycarbonate composition as well as a preparation method and application thereof, and belongs to the field of high polymer materials. Under the combined action of the first polycarbonate with the high melt index, the second polycarbonate with the low melt index, the flame retardant, the polyphenylene sulfone resin, the flexibilizer and the nano silicon dioxide in specific dosage, the polycarbonate composition has good flame retardance, burn-through resistance and heat and humidity resistance; the method is suitable for preparing new energy products, charging panels or office equipment, especially thin-wall products in the new energy products, the charging panels or the office equipment.

Description

Technical Field

[0001] The present application relates to the field of polymer materials, and in particular to a polycarbonate composition and a preparation method and application thereof. Background Art

[0002] Flame-retardant polycarbonate compositions have the advantages of good flame retardancy, high toughness, high heat resistance, etc., and are widely used in new energy, household appliances, charging cabinets and other fields. As people's awareness of fire safety gradually increases, CQC (China Quality Certification Center) has issued requirements for product burn-through resistance. The specific test method is to cut a sample from the product, burn it on a needle flame test device for 60 seconds, and observe whether burn-through occurs. At present, general flame-retardant PC materials are difficult to achieve the effect of burn-through resistance under thin-wall conditions while ensuring the flame retardant effect, and the moisture and heat resistance is poor. The material performance will significantly decrease after being exposed to high temperature and high humidity for a period of time. Summary of the invention

[0003] Based on the defects of the prior art, the purpose of the present application is to provide a polycarbonate composition and a preparation method and application thereof. The obtained polycarbonate composition not only has good flame retardancy, but also has good burn-through resistance and moisture and heat resistance.

[0004] In order to achieve the above objectives, in a first aspect, the present application provides a polycarbonate composition comprising the following components in parts by weight:

[0005]

[0006] The polycarbonate comprises the following components in parts by weight: 80 to 95 parts of a first polycarbonate and 5 to 20 parts of a second polycarbonate. The first polycarbonate has a melt index of 7 to 20 g / 10 min at a temperature of 300° C. and a load of 1.2 kg, and the second polycarbonate has a melt index of 3 to 6 g / 10 min at a temperature of 300° C. and a load of 1.2 kg.

[0007] The inventors found during the research process that by compounding a first polycarbonate with a high melt index with a second polycarbonate with a low melt index, the first polycarbonate with a high melt index can improve the processing performance of the material, and the second polycarbonate with a low melt index can reduce the viscosity difference between resins and improve the dispersion performance between resins because its viscosity is close to PPSU; the polyphenylene sulfone resin can reduce the droplets when the polycarbonate burns, and cooperate with the second polycarbonate with a low melt index to improve the flame retardancy of the material; nano-silica can accelerate the carbonization of polycarbonate, form a network interpenetrating structure, improve the burn-through resistance of the material, and also improve the moisture and heat resistance of the material.

[0008] The polycarbonate composition, under the joint action of the above-mentioned components in specific amounts, has good flame retardancy, burn-through resistance and moisture and heat resistance, and is suitable for preparing new energy products, charging plates or office equipment, especially thin-walled products among these products, such as products with a thickness of less than 2.0 mm. The specific thickness of the product can be selected as 2 mm, 1.8 mm, 1.5 mm or an interval formed by any two of the above values.

[0009] The melt index of the first polycarbonate and the second polycarbonate can be measured according to ASTM-D1238-2010, with the test conditions being 300° C. and 1.2 kg.

[0010] Preferably, the difference in melt index between the first polycarbonate and the second polycarbonate at a temperature of 300°C and a load of 1.2 kg is 3 to 16 g / 10 min, such as 3 g / 10 min, 5 g / 10 min, 7 g / 10 min, 9 g / 10 min, 11 g / 10 min, 13 g / 10 min, 15 g / 10 min, 16 g / 10 min or an interval formed by any two of the above values.

[0011] The total weight of the first polycarbonate and the polydicarbonate is 100 parts.

[0012] Preferably, the polyphenylene sulfone resin is 14 to 21 parts by weight. When the amount of the polyphenylene sulfone resin is 14 to 21 parts by weight, such as 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 21 parts by weight or an interval formed by any two of the above values, the obtained material has better burn-through resistance and moisture heat resistance.

[0013] Preferably, the nano silicon dioxide is 0.9 to 2.1 parts by weight. When the amount of the nano silicon dioxide is 0.9 to 2.1 parts by weight, such as 0.9 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.7 parts by weight, 2 parts by weight, 2.1 parts by weight or any two of the above values, the resulting material has better burn-through resistance and moisture and heat resistance, and the amount of nano silicon dioxide added is low, and the mechanical properties of the material are better.

[0014] Preferably, the flame retardant includes potassium 3-benzenesulfonylbenzenesulfonate (KSS) and an organophosphorus flame retardant, and the weight ratio of the potassium 3-benzenesulfonylbenzenesulfonate to the organophosphorus flame retardant is 1: (9-22). Compounding potassium 3-benzenesulfonylbenzenesulfonate and the organophosphorus flame retardant in a weight ratio of 1: (9-22) can better synergistically improve the flame retardant properties of the material and the carbonization effect of the polycarbonate. The flame retardant includes potassium 3-benzenesulfonylbenzenesulfonate (KSS) and the organophosphorus flame retardant. The weight ratio of the flame retardant can be selected as 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22 or an interval formed by any two of the above values.

[0015] Preferably, the weight percentage of phosphorus in the organophosphorus flame retardant is greater than 8%, and more preferably, the weight percentage of phosphorus in the organophosphorus flame retardant is 10% to 16%.

[0016] When the weight percentage of phosphorus in the organic phosphorus flame retardant is greater than 8%, especially 10% to 16%, the flame retardant effect is better.

[0017] Preferably, the organophosphorus flame retardant includes at least one of phenoxy cyclotriphosphazene, octylphenoxy cyclotetraphosphazene, decylphenoxy cyclopentaphosphazene, diphenyl phosphate, and bis(p-carboxyphenyl)phenylphosphine oxide.

[0018] Preferably, the polyphenylene sulfone resin has a melt index of 5 to 25 g / 10 min at a temperature of 365° C. and a load of 5.0 kg. More preferably, the polyphenylene sulfone resin has a melt index of 7.5 to 15 g / 10 min at a temperature of 365° C. and a load of 5.0 kg.

[0019] When the melt index of the polyphenylene sulfone resin at a temperature of 365° C. and a load of 5.0 kg is in the range of 5 to 25 g / 10 min, especially 7.5 to 20 g / 10 min, the vertical combustion performance and burn-through resistance of the product can be better improved, and the compatibility with polycarbonate is better.

[0020] The melt index of the polyphenylene sulfone resin can be measured according to ASTM-D1238-2010.

[0021] Preferably, the average particle size of the nano-silicon dioxide is 10-100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm or an interval formed by any two of the above values.

[0022] The average particle size of the nano-silicon dioxide can be measured by the following method: testing is performed using a laser particle size analyzer in accordance with standard ISO 13320-2020.

[0023] Preferably, the nano-silicon dioxide is nano-silicon dioxide coated with silane, and the weight percentage of silane in the nano-silicon dioxide coated with silane is 0.5% to 2%. The use of nano-silicon dioxide coated with silane can make the nano-silicon dioxide more dispersible in polycarbonate, thereby better improving the material's burn-through resistance and moisture-heat resistance.

[0024] Preferably, the silane in the nano-silica with silane coated on the surface includes at least one of 3-(methacryloyloxy)propyltrimethoxysilane and γ-glycidylpropyl-trimethoxysilane.

[0025] In some embodiments, the method for preparing the nano-silicon dioxide with the surface coated with silane comprises the following steps: coating the surface of the nano-silicon dioxide with silane by atomization method to obtain the nano-silicon dioxide with the surface coated with silane.

[0026] Preferably, the weight ratio of the nano-silicon dioxide to silane is 100:(0.5-2).

[0027] In some embodiments, the nano-silica with the surface coated with silane is commercially available.

[0028] The first polycarbonate includes, but is not limited to, at least one of bisphenol A polycarbonate and siloxane copolycarbonate.

[0029] The second polycarbonate includes, but is not limited to, at least one of bisphenol A polycarbonate and siloxane copolycarbonate.

[0030] Preferably, the polycarbonate composition further comprises the following components in parts by weight: 0.1 to 1 part of a lubricant and 0.1 to 1 part of an antioxidant.

[0031] Preferably, the lubricant includes at least one of oxidized polyethylene wax and pentaerythritol stearate.

[0032] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, the weight ratio of the primary antioxidant to the secondary antioxidant is 1:(0.5-1.0), wherein the primary antioxidant is a hindered phenol primary antioxidant, and the secondary antioxidant is a phosphite secondary antioxidant. As an example, the hindered phenol primary antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite secondary antioxidant is tris(2,4-di-tert-butylphenyl) phosphite.

[0033] Preferably, the weight percentage of the polycarbonate in the polycarbonate composition is above 60%, such as 60%, 65%, 70%, 75%, 80%, 85%, 88.8% or an interval formed by any two of the above values.

[0034] In a second aspect, the present application provides a method for preparing the polycarbonate composition, comprising the following steps:

[0035] All raw materials are mixed and dispersed, melt-extruded, and granulated to obtain a polycarbonate composition.

[0036] Preferably, the melt extrusion is carried out in a twin-screw extruder.

[0037] Preferably, the aspect ratio of the twin-screw extruder is (40-48):1, the screw speed is 300-600 r / min, and the melt extrusion temperature is 260-290°C.

[0038] In the third aspect, the present application also provides the use of the polycarbonate composition in new energy products, charging boards or office equipment. Exemplarily, the polycarbonate composition can be used to prepare battery housings, especially high-power battery housings (such as charging power of 100W and above); charging board housings; housings of office equipment such as printers, copiers, and projectors.

[0039] Compared with the prior art, the beneficial effect of the present application is that the polycarbonate composition of the present application, under the combined action of a specific amount of a first polycarbonate with a high melt index, a second polycarbonate with a low melt index, a flame retardant, a polyphenylene sulfone resin, a toughening agent and nano-silica, has good flame retardancy, burn-through resistance and moisture and heat resistance, and is suitable for the preparation of new energy products, charging boards or office equipment, especially thin-walled products among these products, such as products with a thickness of less than 2 mm. DETAILED DESCRIPTION

[0040] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present application in detail, rather than to limit the present application. All other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present application. The experimental reagents and instruments involved in the implementation of this application are all commonly used ordinary reagents and instruments unless otherwise specified. In the present application, the technical features described in an open manner include closed technical schemes composed of the listed features, and also include open technical schemes containing the listed features.

[0041] Each of the following examples and comparative examples provides a polycarbonate composition. The formulations of these polycarbonate compositions are shown in Table 1 and Table 2. Their preparation methods include the following steps: mixing and dispersing all raw materials and feeding them into a twin-screw extruder, melt-extruding, and granulating to obtain a polycarbonate composition;

[0042] The screw length-to-diameter ratio of the twin-screw extruder is 40:1, the screw speed is 450 r / min, and the melt extrusion temperature is 280°C.

[0043] The raw material information used in the above examples and comparative examples is as follows, and unless otherwise specified, they are all commercially available raw materials. In addition, the component raw materials used in each parallel experiment are all of the same kind:

[0044] The first polycarbonate 1: the melt index at a temperature of 300°C and a load of 1.2kg is 20g / 10min, model PCCH8225, manufacturer Cangzhou Dahua;

[0045] The first polycarbonate 2: the melt index at a temperature of 300°C and a load of 1.2kg is 15g / 10min, model LXTY1615T-1, manufacturer Luxi Chemical;

[0046] The first polycarbonate 3: the melt index at a temperature of 300° C. and a load of 1.2 kg is 10 g / 10 min, model PC S-2000, manufacturer Mitsubishi;

[0047] The second polycarbonate 1: the melt index at a temperature of 300°C and a load of 1.2kg is 5g / 10min, model LXTY1605T-1, manufacturer Luxi Chemical;

[0048] Second polycarbonate 2: melt index of 3 g / 10 min at 300° C. and 1.2 kg load, model PC3030PJ, manufacturer DOW;

[0049] The second polycarbonate 3: the melt index at a temperature of 300°C and a load of 1.2kg is 6g / 10min, model PC WY-106BR, manufacturer Lihuayi;

[0050] Potassium 3-phenylsulfonylbenzenesulfonate: Model KSS-FR, manufacturer ARiCHEM;

[0051] Organic phosphorus flame retardant 1: hexaphenoxy cyclotriphosphazene, phosphorus content by weight 13.4%, model GC-PNP, manufacturer Guangzhou Shanghe;

[0052] Organic phosphorus flame retardant 2: diphenyl phosphate, phosphorus content by weight 10.5%, model PX-220, manufacturer Zhejiang Wansheng;

[0053] Organic phosphorus flame retardant 3: resorcinol bis(diphenyl phosphate), phosphorus content by weight 10.5%, model CR-733S , manufacturer Japanese bus;

[0054] Polyphenylene sulfone resin 1: melt index at 365°C and 5.0kg load is 10g / 10min, Golden Hair synthesis;

[0055] Polyphenylene sulfone resin 2: melt index of 5 g / 10 min at 365°C and 5.0 kg load, made by Blonde Synthesis;

[0056] Polyphenylene sulfone resin 3: melt index of 25 g / 10 min at 365°C and 5.0 kg load, made by Blonde Synthesis;

[0057] Toughening agent: silicone-acrylic core-shell rubber, model MR-01, manufacturer: Japan Kanebuchi;

[0058] Nano silicon dioxide 1: The weight percentage of silane is 1.96%, and the average particle size is 10-20 nm. The preparation method is as follows: silane is coated on the surface of nano silicon dioxide with an average particle size of 10-20 nm by atomization method, and the weight ratio of the nano silicon dioxide to the silane is 100:2, so as to obtain nano silicon dioxide with the surface coated with silane, that is, nano silicon dioxide 1, wherein the silane is 3-(methacryloyloxy)propyltrimethoxysilane, model KBM-503, and the manufacturer is Shin-Etsu of Japan;

[0059] Nano silicon dioxide 2: The weight percentage of silane is 0.99%, and the average particle size is 30-40 nm. The preparation method is as follows: silane is coated on the surface of nano silicon dioxide with an average particle size of 30-40 nm by atomization method, and the weight ratio of the nano silicon dioxide to the silane is 100:1, so as to obtain nano silicon dioxide with the surface coated with silane, that is, nano silicon dioxide 2, wherein the silane is 3-(methacryloyloxy)propyltrimethoxysilane, model KBM-503, and the manufacturer is Shin-Etsu of Japan;

[0060] Nano silicon dioxide 3: The weight percentage of silane is 0.50%, and the average particle size is 50-60nm. The preparation method is as follows: silane is coated on the surface of nano silicon dioxide with an average particle size of 50-60nm by atomization method, and the weight ratio of the nano silicon dioxide to the silane is 100:0.5, so as to obtain nano silicon dioxide with the surface coated with silane, that is, nano silicon dioxide 3, wherein the silane is γ-(2,3-epoxypropoxy)propyltrimethoxysilane, model KH560, and the manufacturer is Shanghai Yubo;

[0061] Lubricant: oxidized polyethylene wax, commercially available;

[0062] Antioxidant: a mixture of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris(2,4-di-tert-butylphenyl) phosphite, the weight ratio of the two being 1:1, and both are commercially available.

[0063] The melt indexes of the first polycarbonate, the second polycarbonate and the polyphenylene sulfone resin are all measured according to ASTM-D1238-2010.

[0064] The following performance tests were performed on the polycarbonate compositions of the above examples and comparative examples:

[0065] 1) Flame retardant grade test: refer to UL 94-2018 standard, the test specimen size is 125mm*13mm*1.5 / 2.0 / 2.5mm;

[0066] 2) Needle flame test: Injection molded square plates of 100*100*1.5 / 2.0 / 2.5 / 3.0mm, perform needle flame test according to GB / T 5169.5-2020, select the flame application time of 60 seconds, observe whether it is burned through, the result of burning through is "yes", and the result of not burning through is "no"

[0067] 3) Resistance to damp heat aging: A square plate of 3.2mm*12.7mm*64mm was injection molded and placed in an environmental box at 85°C and 85%RH for 600h for damp heat aging. The 23°C Izod notched impact strength of the material before and after damp heat aging was measured according to ASTM D256-2010, type A. The impact strength retention rate was calculated according to the following formula:

[0068] Impact strength retention rate = impact strength after damp heat aging / impact strength before damp heat aging*100.

[0069] The test results are shown in Table 3.

[0070] Table 1

[0071]

[0072]

[0073] Table 2

[0074] Components / parts by weight Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 First Polycarbonate 1 100 90 90 90 Second polycarbonate 1 25 10 Potassium 3-phenylsulfonylbenzenesulfonate 0.5 0.5 0.5 0.5 Organophosphorus flame retardant 1 7.5 7.5 7.5 7.5 Polyphenylene sulfone resin 1 15 25 15 Toughening agent 4 4 4 4 Nano Silica 1 2 2 2 Lubricants 0.2 0.2 0.2 0.2 Antioxidants 0.2 0.2 0.2 0.2

[0075] Table 3

[0076]

[0077]

[0078] It can be seen from the above data that the polycarbonate compositions of each embodiment of the present application have good flame retardancy, burn-through resistance and moisture and heat resistance. For example, the flame retardancy grade is V-0 when the thickness is 2.0 mm, and the flame retardancy grade is V-2 to V-0 when the thickness is 1.5 mm; the needle flame test is not burned through for 60 seconds when the thickness is 1.5 mm to 2.0 mm; the impact strength retention rate is above 69% after 600 hours under the conditions of 85°C and 85% RH.

[0079] In Comparative Example 1, only the first polycarbonate was added without adding the second polycarbonate, and the flame retardancy, burn-through resistance and moisture-heat resistance of the obtained composition were poor.

[0080] In Comparative Examples 2 to 3, only one of the second polycarbonate and PPSU is added, and the resulting compositions have poor burn-through resistance and moisture-heat resistance, or poor flame retardancy, burn-through resistance and moisture-heat resistance.

[0081] In Comparative Example 4, nano-silicon dioxide was not added, and the resulting composition had poor burn-through resistance and moisture-heat resistance.

[0082] Comparison of Examples 1 to 4 shows that when the amount of the polyphenylene sulfone resin is 14 to 21 parts by weight, the resulting composition has better burn-through resistance and moisture-heat resistance.

[0083] Comparison of Examples 1 and 5 to 7 shows that when the amount of nano-silicon dioxide is 0.9 to 2.1 parts by weight, the resulting composition has better burn-through resistance and moisture-heat resistance, and the amount of nano-silicon dioxide added is lower, resulting in a higher cost-effectiveness.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present application.

Claims

1. A polycarbonate composition, characterized in that It includes the following components by weight: The polycarbonate comprises the following components in parts by weight: 80 to 95 parts of a first polycarbonate and 5 to 20 parts of a second polycarbonate. The first polycarbonate has a melt index of 7 to 20 g / 10 min at a temperature of 300° C. and a load of 1.2 kg, and the second polycarbonate has a melt index of 3 to 6 g / 10 min at a temperature of 300° C. and a load of 1.2 kg.

2. The polycarbonate composition according to claim 1, wherein The polyphenylene sulfone resin is 14 to 21 parts by weight.

3. The polycarbonate composition according to claim 1, characterized in that The nano silicon dioxide is 0.9 to 2.1 parts by weight.

4. The polycarbonate composition according to claim 1, wherein The flame retardant comprises potassium 3-phenylsulfonylbenzenesulfonate and an organic phosphorus flame retardant, and the weight ratio of the potassium 3-phenylsulfonylbenzenesulfonate to the organic phosphorus flame retardant is 1:(9-22).

5. The polycarbonate composition according to claim 4, characterized in that The weight percentage of phosphorus in the organophosphorus flame retardant is greater than 8%; preferably, the weight percentage of phosphorus in the organophosphorus flame retardant is 10% to 16%; more preferably, the organophosphorus flame retardant includes at least one of hexaphenoxy cyclotriphosphazene, resorcinol bis(diphenyl phosphate), and diphenyl phosphate.

6. The polycarbonate composition according to claim 1, wherein The polyphenylene sulfone resin has a melt index of 5 to 25 g / 10 min at a temperature of 365° C. and a load of 5.0 kg.

7. The polycarbonate composition according to claim 1, wherein The nano silicon dioxide meets at least one of the following conditions: S1. The average particle size of the nano-silicon dioxide is 10-100nm; S2. The nano-silicon dioxide is nano-silicon dioxide with a surface coated with silane, and the weight percentage of silane in the nano-silicon dioxide with a surface coated with silane is 0.5% to 2%.

8. The polycarbonate composition according to claim 1, wherein The polycarbonate composition satisfies at least one of the following conditions: S4. The toughening agent includes a silicone rubber toughening agent; S5. The polycarbonate composition further comprises the following components in parts by weight: 0.1 to 1 part of a lubricant and 0.1 to 1 part of an antioxidant.

9. The method for preparing a polycarbonate composition according to any one of claims 1 to 8, characterized in that: All raw materials are mixed and dispersed, melt-extruded, and granulated to obtain a polycarbonate composition.

10. Use of the polycarbonate composition according to any one of claims 1 to 8 in new energy products, charging boards or office equipment.

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