PC / PS composite material, preparation method and application thereof

Abstract

The application provides a PC / PS composite material and a preparation method and application thereof, and belongs to the technical field of polymer materials. The PC / PS composite material comprises the following components in parts by weight: polycarbonate 75-105 parts, polystyrene 7-26 parts, and composite compatilizer 2-10 parts. The composite compatilizer comprises a first compatilizer and a second compatilizer, and the mass ratio of the first compatilizer to the second compatilizer is 5.5-8:2-4.5. The first compatilizer is a polyphenylene ether-maleic anhydride graft polymer and a polystyrene graft maleic anhydride copolymer, and the second compatilizer is a styrene-acrylonitrile graft glycidyl methacrylate. The application introduces specific types and proportions of compatilizers into the PC / PS system to obtain a PC / PS composite material with high compatibility, hardness, interlayer bonding strength, elongation at break, fluidity and solvent resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a PC / PS composite material and a preparation method and application thereof. BACKGROUND

[0002] Polycarbonate (PC) is an amorphous, odorless, tasteless, nontoxic, transparent thermoplastic polymer. PC has excellent impact toughness, transparency, dimensional stability, creep resistance, weather resistance, electrical insulation and other advantages, but it is sensitive to notches, poor in environmental stress cracking, high in melt viscosity, poor in flowability and poor in processing performance. By blending polyolefin (PS) with PC, the viscosity of PC can be effectively reduced, and the forming and processing performance thereof can be improved.

[0003] Polycarbonate / polystyrene alloy material can combine the characteristics of polystyrene and polystyrene, obtain balanced mechanical properties and heat resistance, and is easy to form and process. However, PS and PC molecular chains both contain a large number of benzene ring structures, and have large steric hindrance. Polystyrene material and polycarbonate material have poor alloy compatibility, and have defects such as part peeling, layering and poor mechanical properties. In order to improve the compatibility and improve the comprehensive performance of the PC / PS composite material, a compatibilizer is usually added. Patent CN112322015A discloses a polycarbonate / polystyrene alloy. By selecting polystyrene with a specific rubber distribution particle size, and adding a carboxylic acid-based ionomer, the structure of the polycarbonate and polystyrene alloy is changed, and the dielectric loss is reduced. Patent CN114230998A discloses a PC / PS / PMMA ternary alloy material and a preparation method thereof. A mixture of sub-phosphorylated tris-caprolactam and glycidyl methacrylate in a weight ratio of 2.3-3:1.2-1.5 is used as a compatibilizer to improve the scratch resistance and wear resistance of the alloy. Patent CN105820529A discloses a polycarbonate / polystyrene alloy material and a preparation method thereof. PS-g-GMA, PS-g-MAH, SEBS-g-MAH and other compatibilizers are used to improve the processing flowability and impact resistance of the alloy material. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art, and provides a PC / PS composite material. The PC / PS composite material has high compatibility, hardness, interlayer bonding strength, elongation at break, flowability and solvent resistance, and is suitable for preparing an energy storage cover plate.

[0005] To achieve the above object, the technical scheme adopted by the present application is: on the one hand, a PC / PS composite material is provided, comprising the following components by weight: polycarbonate 75-105 parts, polystyrene 7-26 parts, and composite compatibilizer 2-10 parts; the composite compatibilizer comprises a first compatibilizer and a second compatibilizer, and the mass ratio of the first compatibilizer to the second compatibilizer is 5.5-8:2-4.5; the first compatibilizer is polyphenylene ether-maleic anhydride graft polymer (PPO-g-MAH) and SEBS-g-MAH, and the second compatibilizer is styrene-acrylonitrile grafted glycidyl methacrylate (SAN-g-GMA).

[0006] In this document, the mass ratio of the first compatibilizer to the second compatibilizer can be, but is not limited to, 5.5:4.5, 6:4, 6.5:3.5, 7:3, 7.5:2.5, 8:2, and is preferably 6-7:3-4.

[0007] In the technical scheme of the present application, the PC / PS composite material is compounded with specific different compatibilizers, effectively improving the hardness, solvent resistance, compatibility and flowability of the product; the styrene-acrylonitrile grafted glycidyl methacrylate is mainly distributed in the PS phase, and needs a period of time to migrate to the interface and react with the PC end group; the active groups of the styrene-acrylonitrile grafted glycidyl methacrylate react with the terminal hydroxyl and carboxyl groups in the PC molecular chain to form a PC-g-ester / ether structure, which improves the polarity of PS and thus improves the compatibility and flowability of the PC / PS composite material; in addition, the macromolecular segments in the styrene-acrylonitrile grafted glycidyl methacrylate are in the PS phase, which improves the ductility of the PC / PS composite material; the first compatibilizer is mainly distributed in the PC phase, and the maleic anhydride can react with the hydroxyl groups in PC to form a PC-g-ester / ether structure, which is inserted in the PC interior and interface, and the SEBS molecular chain part in SEBS-g-MAH is inserted in the PS phase, thereby improving the compatibility of the product; the mutual entanglement of the PPO molecular chain in PPO-g-MAH and the PC molecular chain reduces the agglomeration of SEBS-g-MAH in the PC phase, and improves the hardness and solvent resistance of the PC / PS composite material.

[0008] If the content of styrene-acrylonitrile grafted glycidyl methacrylate is too much, the compatibility of the product does not improve obviously. On the one hand, too much styrene-acrylonitrile grafted glycidyl methacrylate can cause incomplete reaction of glycidyl ester, and the reaction activity of the glycidyl group is high, which leads to crosslinking reaction and reduces the flowability of the PC / PS composite material. On the other hand, the unreacted styrene-acrylonitrile grafted glycidyl methacrylate can migrate and penetrate into the interface, block the contact between the maleic anhydride and the PS, and at the same time, destroy the reaction activity of the maleic anhydride graft, which leads to the decrease of the hardness and solvent resistance of the product. In the present application, the mass ratio of the first compatibilizer and the second compatibilizer is preferably 6-7:3-4, so as to obtain a PC / PS composite material with good comprehensive performance.

[0009] In an embodiment, the mass ratio of the polyphenylene ether-maleic anhydride graft polymer and SEBS-g-MAH is 1:1-3, for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.3, 1:2.5, 1:2.7, 1:3, and the present application is not limited thereto; preferably, it is 1:1.5-3. The mass ratio of the polyphenylene ether-maleic anhydride graft polymer and SEBS-g-MAH has an influence on the hardness, compatibility, elongation at break and solvent resistance of the product. It has been verified that when the mass ratio of the polyphenylene ether-maleic anhydride graft polymer and SEBS-g-MAH is within the above range, the product can obtain higher hardness, compatibility, elongation at break and solvent resistance. If the addition amount of PPO-g-MAH is too small, it is difficult to reduce the agglomeration of SEBS-g-MAH in the PC phase, which leads to the decrease of the hardness and solvent resistance of the PC / PS composite material. If the addition amount of PPO-g-MAH is too much, the content of PPO molecular chain in the PS phase increases, which leads to a certain degree of decrease of the compatibility and ductility of the product.

[0010] In an embodiment, the weight part of the polycarbonate can be 75 parts, 80 parts, 83 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 97 parts, 100 parts, 102 parts, 105 parts, but is not limited to the listed values, and other values within the scope of the present disclosure are also applicable.

[0011] In an embodiment, the grafting rate of maleic anhydride in the first compatibilizer is 1-3%, for example, it can be 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, and the present application is not limited thereto.

[0012] In one embodiment, the grafting rate of glycidyl methacrylate in the second compatibilizer is 0.5-10%, for example, it can be 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.3%, 3.5%, 4.0%, 4.5%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10%, the present application is not limited thereto.

[0013] In the present application, the grafting rate of maleic anhydride in the first compatibilizer affects the performance of the product. If the grafting rate of maleic anhydride in the first compatibilizer is too high, crosslinking reaction will occur, and the flowability of the product will decrease. If the grafting rate of maleic anhydride in the first compatibilizer is too low, the content of reactive groups will decrease, and the compatibility, ductility and solvent resistance of the product will decrease to a certain extent.

[0014] In the present application, the grafting rate of maleic anhydride in the first compatibilizer is tested by acid-base titration method.

[0015] The grafting rate of glycidyl methacrylate in the second compatibilizer is tested by acid-base titration method.

[0016] In one embodiment, the polystyrene is high impact polystyrene, and the melt flow rate of the high impact polystyrene is 3-6 g / 10 min according to ASTM D1238 standard at 200℃ and 5 kg.

[0017] Optionally, in the PC / PS composite material, the sum of the mass percentage of the polycarbonate and the polystyrene is not less than 90%;

[0018] In the PC / PS composite material, the mass of the polycarbonate is preferably not less than 50%;

[0019] In one embodiment, the polycarbonate is preferably bisphenol A type polycarbonate, and the melt flow rate of the bisphenol A type polycarbonate is 5-20 g / 10 min according to ASTM D1238 standard at 300℃ and 1.2 kg.

[0020] In the present application, the weight part of the polystyrene can be 7 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 26 parts, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0021] In the present application, the weight part of the composite compatibilizer can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0022] In one embodiment, the PC / PS composite material comprises 0.1-0.5 parts by weight of triethanolamine, for example, can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, and the present disclosure is not limited thereto.

[0023] In the present application, the hydroxyl group in triethanolamine interacts with PC and PS, enhances the cross-linking of PC and PS, and improves the interlayer bonding strength and solvent resistance of the PC / PS composite material.

[0024] In one embodiment, the PC / PS composite material further comprises 0.1-2.0 parts by weight of a flame retardant and 0.1-2.0 parts of an antioxidant.

[0025] In one embodiment, the flame retardant is an organic phosphorus flame retardant, for example, bisphenol A bis(diphenyl phosphate) (BDP).

[0026] In one embodiment, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0027] In another aspect, the present application provides a preparation method of the PC / PS composite material, comprising the following steps: uniformly mixing the components in proportion, adding the obtained premix into an extruder, and performing melting, extrusion, and granulation to obtain the PC / PS composite material.

[0028] In one embodiment, the mixing temperature is 50-70℃, the rotation speed is 300-500 r / min, and the time is 3-5 min; and / or the temperature of the extruder is 190-270℃, and the rotation speed is 180-400 r / min.

[0029] In still another aspect, the present application provides the use of the PC / PS composite material in the preparation of an energy storage cover plate.

[0030] The PC / PS composite material provided by the present application has excellent compatibility, hardness, interlayer bonding strength, elongation at break, flowability, and solvent resistance, and is very suitable for the application requirements of an energy storage cover plate.

[0031] Compared with the prior art, the beneficial effects of the application are: in the technical scheme of the application, the PC / PS composite is compounded with specific different compatilizers, effectively improving the hardness, solvent resistance, compatibility and fluidity of the product, the styrene-acrylonitrile grafted glycidyl methacrylate is mainly distributed in the PS phase, and needs a period of time to migrate to the interface and react with the PC end group, the epoxy active group in the styrene-acrylonitrile grafted glycidyl methacrylate reacts with the end hydroxyl and end carboxyl in the PC molecular chain to form a PC-g-ester / ether structure, which plays a role in improving the polarity of PS, thereby improving the compatibility and fluidity of the PC / PS composite, in addition, the macromolecular chain segment in the styrene-acrylonitrile grafted glycidyl methacrylate is in the PS phase, which improves the ductility of the PC / PS composite; the first compatilizer is mainly distributed in the PC phase, the maleic anhydride can react with the hydroxyl group in PC to form a PC-g-ester / ether structure, which is inserted in the PC interior and interface, and the SEBS molecular chain part in the SEBS-g-MAH is inserted in the PS phase, thereby improving the compatibility of the product; the mutual entanglement of the PPO molecular chain in the PPO-g-MAH and the PC molecular chain reduces the agglomeration of the SEBS-g-MAH in the PC phase, and improves the hardness and solvent resistance of the PC / PS composite. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 A schematic diagram for testing the solvent resistance of the PC / PS composite of the application. DETAILED DESCRIPTION

[0033] In order to better illustrate the purpose, technical scheme and advantages of the application, the application will be further described below in combination with specific examples and comparative examples, the purpose of which is to understand the content of the application in detail, rather than to limit the application. All other examples obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the application. The experimental reagents and instruments involved in the implementation of the application are common ordinary reagents and instruments unless otherwise specified.

[0034] The raw materials used in the examples and comparative examples are described as follows, but are not limited to these materials:

[0035] Polycarbonate: the melt flow rate at 300℃, 1.2kg according to ASTM D1238 standard is 10g / min, PC 1300-10NP, LG Chemical;

[0036] Polystyrene: the melt flow rate at 200℃, 5kg according to ASTM D1238 standard is 5g / min, HIPS-622, Shanghai Sike;

[0037] PPO-g-MAH-1: grafting rate of maleic anhydride is 1.2%, PO-1 Dongguan Jingke High Polymer Co., Ltd.

[0038] PPO-g-MAH-2: grafting rate of maleic anhydride is 3%, GPM 450C, Ningbo Nengzhiguang;

[0039] SEBS-g-MAH: grafting rate of maleic anhydride is 1.8%, SEBS 7131, Taiwan Tai Xiang;

[0040] SAN-g-GMA-2: SAG-002, Jia Yirong;

[0041] SAN-g-GMA-3: ST-SAG2030, Xingbeida;

[0042] Triethanolamine: commercially available;

[0043] Flame retardant: bisphenol A-bis(diphenyl phosphate), commercially available;

[0044] Antioxidant: antioxidant 1068, commercially available.

[0045] Examples and comparative examples

[0046] The components and weight parts of the PC / PS composite material of the examples and comparative examples are shown in Table 1 and Table 2, wherein the preparation method of the PC / PS composite material of the examples and comparative examples comprises the following steps:

[0047] (1) weighing various components according to the proportion;

[0048] (2) mixing the first compatibilizer and the second compatibilizer uniformly to obtain a composite compatibilizer; mixing the composite compatibilizer, polycarbonate, polystyrene, triethanolamine, flame retardant, antioxidant at a temperature of 60°C and a rotation speed of 300r / min for 5min to obtain a premix;

[0049] (3) conveying the premix obtained in step (2) into a double screw extruder, the temperature of each section of the screw of the double screw extruder is 190-270°C, and the rotation speed is 300r / min, melt extrusion granulation to obtain the PC / PS composite material.

[0050] Table 1

[0051]

[0052] Table 2

[0053]

[0054] Performance test:

[0055] The PC / PS composite materials obtained in the examples and comparative examples were injection molded into standard bars, which were then tested.

[0056] (1) Hardness: measured according to ASTM D2240 at room temperature using LS-A rubber Shore A durometer;

[0057] (2) Elongation: measured according to ASTM D412 at 60°C at a speed of 50 mm / min using a universal testing machine to measure the elongation at break;

[0058] (3) Melt index: measured according to ASTM D1238 using a melt flow rate instrument at a test temperature of 200°C and a test load of 5 kg;

[0059] (4) Compatibility test: the sample was injection molded into a bar of 12.5 mm*4 mm*1.2 mm, head-to-tail alignment, and folded once in both directions for one cycle, and the number of times of breaking and the state were recorded, and the compatibility grade is shown in Table 3.

[0060] (5) Solvent resistance:

[0061] Mold: steel mold, inner length 165 mm;

[0062] Sample: tensile sample prepared according to ISO527 standard, length 169 mm;

[0063] Chemical reagent: engine oil;

[0064] Evaluation method: as shown in Figure 1 , the chemical was uniformly coated on the upper surface of the sample at the highest bending point of the sample, and then the time of breaking of the sample was recorded as the standard for evaluating the chemical resistance of the material.

[0065] (6) Interlayer bonding strength: measured according to ASTM D412 at 23°C at a speed of 50 mm / min using a universal testing machine, if the fracture is neat, the interlayer bonding strength = tensile strength, if delamination occurs, the interlayer bonding strength = 0.8*tensile strength.

[0066] The test results are shown in Tables 4 and 5.

[0067] Table 3

[0068]

[0069] Table 4

[0070]

[0071] Table 5

[0072]

[0073] From the experimental data of Table 4-5, it can be seen that the PC / PS composite of the present application has excellent compatibility, hardness, interlayer bonding strength, elongation at break, flowability and solvent resistance.

[0074] From the comparison of Examples 1-4 and Comparative Examples 4-5, it can be seen that when the mass ratio of the first compatibilizer and the second compatibilizer deviates from the scope of the present application, the hardness, compatibility, elongation at break, flowability and solvent resistance of the product all decrease; in Comparative Example 4, the content of the first compatibilizer is too high, and the hardness, elongation at break and solvent resistance decrease; in Comparative Example 5, the content of the second compatibilizer is too high, and the flowability, hardness and solvent resistance decrease.

[0075] When the mass ratio of the first compatibilizer and the second compatibilizer is 6-7:3-4, the compatibility, flowability, elongation at break, hardness and solvent resistance of the product increase.

[0076] From the comparison of Example 1 and Examples 5-7, it can be seen that when the mass ratio of the polyphenylene ether-maleic anhydride grafting polymer and SEBS-g-MAH is 1:1.5-3, the compatibility, hardness, interlayer bonding strength, elongation at break, flowability and solvent resistance of the product increase. In Example 7, the content of the polyphenylene ether-maleic anhydride grafting polymer is too high, and the hardness and solvent resistance decrease.

[0077] From the comparison of Example 1 and Example 10, it can be seen that the addition of triethanolamine can increase the interlayer bonding strength and solvent resistance of the PC / PS composite.

[0078] From Example 1 and Comparative Examples 1-3, it can be seen that when at least one of the first compatibilizer or the second compatibilizer is absent, the performance of the product decreases significantly.

[0079] From Example 1 and Comparative Examples 4-5, it can be seen that when the mass ratio of the first compatibilizer and the second compatibilizer is not within the scope of the present application, the performance of the product decreases significantly.

[0080] Finally, it should be noted that the above examples are used to illustrate the technical solutions of the present application and not 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, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A PC / PS composite material, characterized by, The PC / PS composite material comprises the following components by weight: polycarbonate 75-105 parts, polystyrene 7-26 parts, and composite compatibilizer 2-10 parts; the composite compatibilizer comprises a first compatibilizer and a second compatibilizer, and the mass ratio of the first compatibilizer to the second compatibilizer is 5.5-8:2-4.5; the first compatibilizer is polyphenylene ether-maleic anhydride graft polymer and SEBS-g-MAH, and the second compatibilizer is styrene-acrylonitrile grafted glycidyl methacrylate; wherein the mass ratio of the polyphenylene ether-maleic anhydride graft polymer to SEBS-g-MAH is 1:1-3.

2. The PC / PS composite of claim 1, wherein, The mass ratio of the first compatibilizer to the second compatibilizer is 6-7:3-4.

3. The PC / PS composite of claim 1, wherein, The grafting rate of maleic anhydride in the first compatibilizer is 1-3%.

4. The PC / PS composite of claim 1, wherein The PC / PS composite material comprises 0.1-0.5 parts by weight of triethanolamine.

5. The PC / PS composite of claim 1, wherein, The PC / PS composite material further comprises 0.1-2.0 parts by weight of a flame retardant and 0.1-2.0 parts of an antioxidant.

6. The PC / PS composite of claim 5, wherein, The flame retardant is an organic phosphorus flame retardant; and the antioxidant is at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168.

7. A process for the production of a PC / PS composite material as claimed in any one of claims 1 to 6, characterized in that The PC / PS composite material is prepared by the following steps: uniformly mixing the components in proportion, adding the obtained premix into an extruder, and then melting, extruding, and granulating to obtain the PC / PS composite material.

8. The production method according to claim 7, wherein The mixing is performed at a temperature of 50-70°C, a rotation speed of 300-500 r / min, and a time of 3-5 min; and / or the temperature of the extruder is 190-270°C, and the rotation speed is 180-400 r / min.

9. Use of the PC / PS composite material according to any one of claims 1-6 in the preparation of an energy storage cover plate.

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