Solvent-resistant flame-retardant PC / PBT alloy material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and provides a solvent-resistant flame-retardant PC / PBT alloy material which comprises PC, PBT, a flexibilizer, a flame retardant, a transesterification inhibitor and an antioxidant. The mass ratio of the PC to the PBT is (4-6): 1; on the basis that the sum of the mass of the PC and the mass of the PBT is 100 parts, the toughening agent accounts for 8-30 parts, the flame retardant accounts for 13-17 parts, the ester exchanger accounts for 0.5-3 parts, and the antioxidant accounts for 0.01-0.3 part; the toughening agent comprises a toughening compatilizer and a silicon-containing toughening agent. The solvent-resistant flame-retardant PC / PBT alloy material provided by the invention effectively solves the problem of poor solvent resistance of a high-PC-content PC / PBT alloy, has excellent solvent resistance, normal-temperature and low-temperature impact resistance, flame retardance and processability, can be widely applied to the field with relatively high requirements on solvent resistance, flame retardance and mechanical properties, and is simple in production process and low in cost. The method is very suitable for industrial production and has a good market prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more specifically to a solvent-resistant and flame-retardant PC / PBT alloy material and a preparation method thereof. Background Art

[0002] PC / PBT alloy material is a blended alloy made of PC (polycarbonate) and PBT (polybutylene terephthalate). Among them, PC has excellent impact resistance and heat resistance, high strength and elastic coefficient, and low forming shrinkage. Increasing the PC content in PC / PBT alloy materials can effectively improve the mechanical properties, heat resistance and dimensional stability of the alloy materials. However, due to the poor solvent resistance of PC, the solvent resistance of PC / PBT alloy materials with high PC content is not ideal, and stress cracking and swelling are prone to occur under solvent conditions, which limits the application scope of PC / PBT alloy materials. By increasing the PBT content in PC / PBT alloy materials, the solvent resistance of the alloy material can be improved to a certain extent, but at the same time it will cause a significant decrease in mechanical properties, heat resistance and flame retardant properties.

[0003] Therefore, how to improve the solvent resistance of PC / PBT alloy materials with high PC content is an urgent problem to be solved. Summary of the invention

[0004] The object of the present invention is to provide a solvent-resistant and flame-retardant PC / PBT alloy material to solve the technical problem of poor solvent resistance of PC / PET alloy materials with high PC content in the prior art.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] In a first aspect, the present invention provides a solvent-resistant flame-retardant PC / PBT alloy material, comprising PC, PBT, a toughening agent, a flame retardant, an ester exchange inhibitor and an antioxidant;

[0007] The mass ratio of PC to PBT is (4-6):1; based on 100 parts of the sum of the mass of PC and PBT, the toughening agent is 8-30 parts, the flame retardant is 13-17 parts, the transesterification agent is 0.5-3 parts, and the antioxidant is 0.01-0.3 parts;

[0008] The toughening agent includes a toughening compatibilizer and a silicon-containing toughening agent.

[0009] The solvent-resistant flame-retardant PC / PBT alloy material provided by the present invention can effectively improve the solvent resistance of the PC / PBT alloy material with a high PC content by adopting a technical solution of using a toughening compatibilizer and a silicon-containing toughening agent in combination.

[0010] According to some embodiments of the present invention, the toughening compatibilizer contains a structure of glycidyl methacrylate.

[0011] According to some embodiments of the present invention, the toughening compatibilizer includes ethylene-methyl acrylate-glycidyl methacrylate and / or ethylene-butyl acrylate-glycidyl methacrylate.

[0012] According to some embodiments of the present invention, the silicon-containing toughening agent is a core-shell structure toughening agent with a cross-linked acrylate and silicone copolymer as the core and a grafted polymethyl methacrylate as the shell, such as S-2001, S-2051, S-2030, S-2050, S-2200 and other silicon-containing toughening agents with the above core-shell structure produced by Mitsubishi Corporation of Japan.

[0013] According to some embodiments of the present invention, the mass ratio of the toughening compatibilizer to the silicon-containing toughening agent is (5.5-7):1.

[0014] According to some embodiments of the present invention, the PC has a melt index of 5 to 20 g / min at 250° C. and 5 kg.

[0015] According to some embodiments of the present invention, the intrinsic viscosity of the PBT at 25° C. is 0.8 to 1.3 dL / g.

[0016] According to some embodiments of the present invention, the flame retardant is a brominated flame retardant.

[0017] In the present invention, a brominated flame retardant is selected, which has good compatibility with the PC / PBT alloy material and has little effect on its mechanical properties, and can greatly improve its flame retardant properties without reducing the impact resistance of the PC / PBT alloy material. Compared with other flame retardants, it can effectively avoid adverse effects on the mechanical properties of the PC / PBT alloy material.

[0018] According to some embodiments of the present invention, the flame retardant includes phenoxytetrabromobisphenol A carbonate oligomer and / or tris(tribromophenoxy)triazine.

[0019] According to some embodiments of the present invention, the transesterification inhibitor includes at least one of ESC-PGP, sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, sodium pyrophosphate, and triphenyl phosphite.

[0020] In the present invention, the sodium dihydrogen phosphate is preferably anhydrous sodium dihydrogen phosphate.

[0021] According to some embodiments of the present invention, the antioxidant includes at least one of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), and tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168).

[0022] In a second aspect, the present invention provides a method for preparing the PC / PBT alloy material described in the first aspect, comprising: mixing the components, passing them into a twin-screw granulator, melt-extruding at 190-260° C., cooling, and pelletizing to obtain the solvent-resistant and flame-retardant PC / PBT alloy material.

[0023] According to some embodiments of the present invention, the output of the melt extrusion is 300-600 kg / h.

[0024] According to some embodiments of the present invention, the PC and PBT are dried before the components are mixed.

[0025] According to some embodiments of the present invention, PC and PBT are dried to a moisture content of ≤ 250 ppm.

[0026] The beneficial effects of the present invention are at least:

[0027] The solvent-resistant and flame-retardant PC / PBT alloy material provided by the present invention effectively solves the problem of poor solvent resistance of PC / PBT alloys with a high PC content, has excellent solvent resistance, room temperature and low temperature impact resistance, flame retardancy and processing performance, can be widely used in fields with high requirements for solvent resistance, flame retardancy and mechanical properties, and has a simple production process, is very suitable for industrial production, and has good market prospects. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain this patent in detail and do not limit the scope of protection of the present invention in any way.

[0029] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples, etc., can all be purchased on the market or can be obtained by existing methods; the reagent amounts, unless otherwise specified, are the reagent amounts used in conventional experimental operations; the experimental methods, unless otherwise specified, are all conventional methods.

[0030] In each embodiment and comparative example of the present invention, each performance data is tested according to the following test method:

[0031] Tensile strength test: carried out according to ASTM D638 standard.

[0032] Bending strength test: carried out according to ASTM D790 standard.

[0033] Notched impact strength test: carried out according to ASTM D256 standard.

[0034] Vertical burning rating test: carried out in accordance with UL94 standard.

[0035] Solvent resistance test: According to GB / T11547-2008 standard, the organic solvent used in the test is electronic cleaning agent ENIENTEC0101.

[0036] In various embodiments and comparative examples of the present invention, the materials used are as follows:

[0037] PC: PC-141R, SABIC.

[0038] PBT: PBT-1100A, Changchun Chemical Company, Taiwan, China.

[0039] Brominated flame retardant: BC-58 (phenoxy tetrabromobisphenol A carbonate oligomer), Great Lakes, USA.

[0040] Ester exchange inhibitor: ESC-PGP, Nanjing Fuju Chemical Co., Ltd.

[0041] Toughening compatibilizer: ethylene-methyl acrylate-glycidyl methacrylate, Arkema, France.

[0042] Silicon-containing toughening agent: S2030, Mitsubishi Corporation of Japan.

[0043] Antioxidant: Irganox1076:Irganox168=2:1, BASF.

[0044] The raw materials were weighed according to the raw material components and their proportions shown in Table 1, and the PC / PBT alloy materials of each embodiment and each comparative example were prepared according to the following method:

[0045] (1) Dry PC and PBT in a dehumidifying dryer for 3 to 4 hours to make their water content ≤250ppm;

[0046] (2) adding each raw material component into a 200 L high-speed mixer, mixing for 2 min at high speed mode and for 3 min at low speed mode to obtain a uniform mixture;

[0047] (3) The uniform mixture obtained in step (2) is added into the main barrel of an RXT-65 twin-screw extruder for melt extrusion. The processing technology of the twin-screw extruder is as follows: the processing temperature of the twin-screw extruder is 190-280° C. The extruder includes seven temperature zones, wherein the first zone is 190° C., the second zone is 220° C., the third zone is 230° C., the fourth zone is 240° C., the fifth zone is 250° C., the sixth zone is 250° C., and the seventh zone is 245° C. The screw speed is 500 r / min and the output is 500 kg / h; the material strips are cooled in a water trough and pelletized to obtain PC / PBT alloy material.

[0048] Table 1

[0049]

[0050] The PC / PBT alloy materials prepared in the examples and comparative examples were dried at 120°C for 2h and injection molded into ASTM standard specimens by an injection molding machine. The temperatures of each section of the injection molding machine were 230, 240, and 250°C, the nozzle temperature was 250°C, and the hot runner temperature was 260°C.

[0051] The properties of the injection molded specimens were tested after being placed at 50% relative humidity and 23°C for 24 hours, and the low-temperature notched impact strength was tested after being placed at -40°C for 3 hours.

[0052] The performance test results are shown in Table 2.

[0053] Table 2

[0054]

[0055]

[0056] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A solvent-resistant flame-retardant PC / PBT alloy material, characterized in that: Including PC, PBT, toughening agent, flame retardant, transesterification inhibitor and antioxidant; The mass ratio of PC to PBT is (4-6):1; based on 100 parts of the sum of the mass of PC and PBT, the toughening agent is 8-30 parts, the flame retardant is 13-17 parts, the transesterification agent is 0.5-3 parts, and the antioxidant is 0.01-0.3 parts; The toughening agent includes a toughening compatibilizer and a silicon-containing toughening agent.

2. The PC / PBT alloy material according to claim 1, characterized in that: The toughening compatibilizer contains the structure of glycidyl methacrylate; preferably, the toughening compatibilizer includes ethylene-methyl acrylate-glycidyl methacrylate and / or ethylene-butyl acrylate-glycidyl methacrylate; And / or, the silicon-containing toughening agent is a core-shell structure toughening agent with a cross-linked acrylate and silicone copolymer as a core and grafted polymethyl methacrylate as a shell.

3. The PC / PBT alloy material according to claim 1 or 2, characterized in that: The mass ratio of the toughening compatibilizer to the silicon-containing toughening agent is (5.5-7):

1.

4. The PC / PBT alloy material according to any one of claims 1 to 3, characterized in that: The flame retardant is a brominated flame retardant.

5. The PC / PBT alloy material according to claim 4, characterized in that: The flame retardant includes phenoxy tetrabromobisphenol A carbonate oligomer and / or tris(tribromophenoxy)triazine.

6. The PC / PBT alloy material according to any one of claims 1 to 5, characterized in that: The ester exchange inhibitor includes at least one of ESC-PGP, sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, sodium pyrophosphate, and triphenyl phosphite.

7. The PC / PBT alloy material according to any one of claims 1 to 6, characterized in that: The antioxidant includes at least one of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and tris(2,4-di-tert-butylphenyl) phosphite.

8. The method for preparing the PC / PBT alloy material according to any one of claims 1 to 7, characterized in that: include: After the components are mixed, they are introduced into a twin-screw granulator, melt-extruded at 190-260° C., cooled, and pelletized to obtain the solvent-resistant and flame-retardant PC / PBT alloy material.

9. The preparation method according to claim 8, characterized in that: The PC and PBT were dried before mixing the components.

10. The preparation method according to claim 9, characterized in that: PC and PBT were dried to a moisture content of ≤250ppm.

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