Preparation method and application of flame-retardant reinforced PC-PBT alloy material

Abstract

The invention provides a preparation method and application of a flame-retardant reinforced PC-PBT (polycarbonate-polybutylene terephthalate) alloy material. The PC-PBT alloy material is prepared from the following components in parts by weight: 20 to 60 parts of PC, 20 to 60 parts of PBT, 5 to 50 parts of reinforcing filler, 5 to 12 parts of flame retardant, 0.1 to 3 parts of flame-retardant synergist, 0.1 to 2 parts of terminal olefine acid ester, 0.1 to 2 parts of flexibilizer, 0.5 to 5 parts of coupling agent, 0.01 to 5 parts of antioxidant and 0.01 to 5 parts of lubricant. The preparation method comprises the following steps: weighing the raw material components in parts by weight, adding the raw material components into a high-speed mixer, and uniformly mixing and stirring; putting the mixture into an extruder for melting and mixing; a melt obtained after mixing is extruded through an extruder, and the flame-retardant reinforced PC-PBT alloy material is obtained. According to the flame-retardant reinforced PCPBT alloy material, PC and PBT materials are compounded, ester exchange reaction of PC and PBT is further inhibited through the terminal olefine acid ester auxiliary agent, the flame-retardant reinforced PCPBT alloy material with good mechanical performance is obtained, the requirements of workpieces such as electric control boxes and battery modules of peripheral materials of an electric control system can be met, and the flame-retardant reinforced PCPBT alloy material can be applied to the manufacturing industry of new energy automobiles, electronic and electrical appliances and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material modification, and in particular to a preparation method and application of a low flame retardant reinforced PC-PBT alloy material. Background Art

[0002] Polycarbonate (PC) has good toughness, excellent creep resistance, heat resistance and good dielectric properties. It is one of the five general engineering plastics and is widely used in automobiles, electronics, machinery and other fields.

[0003] PBT is a linear saturated polyester with high crystallinity. It has excellent mechanical properties, chemical resistance, easy molding and low moisture absorption. It is a thermoplastic engineering plastic with excellent comprehensive properties.

[0004] However, PBT materials have disadvantages such as low Tg temperature, large molding shrinkage, and high notch sensitivity. Compounding PC with PBT materials can effectively improve the mechanical properties of the materials, especially toughness, but PC and PBT are prone to transesterification, which hinders the effective crystallization of PBT and affects the heat resistance of the material. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a flame retardant reinforced PC-PBT alloy material which can effectively inhibit ester exchange reaction and has excellent mechanical properties.

[0006] To achieve the above object, the present invention provides a method for preparing a flame retardant reinforced PC-PBT alloy material, wherein the PC-PBT alloy material is composed of the following components in parts by weight:

[0007] PC: 20-60 parts, PBT: 20-60 parts, reinforcing filler: 5-50 parts, flame retardant: 5-12 parts, flame retardant synergist: 0.1-3 parts, terminal olefin ester: 0.1-2 parts, toughening agent: 0.1-2 parts, coupling agent: 0.5-5 parts, antioxidant: 0.01-5 parts, lubricant: 0.01-5 parts;

[0008] The preparation method of the PC-PBT alloy material comprises:

[0009] Step 1: Weigh the raw material components according to the weight ratio, and pre-dry the materials before mixing at a temperature of 85-100°C.

[0010] Step 2: Add the dried raw materials into a high-speed mixer and mix and stir evenly;

[0011] Preferably, the mixing rotation speed is 300-700 rpm, for example, it can be 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm or 650 rpm, and specific values ​​between the above points.

[0012] Preferably, the mixing time is 3-15 min, for example, 4 min, 5 min, 6 min, 8 min, 10 min, 12 min or 14 min, and specific values ​​between the above points.

[0013] Step 3: feeding the mixture into an extruder, and melt-kneading at 240-270° C., wherein the melt-kneading temperature may be 245° C., 250° C., 255° C., 260° C., 265° C., and specific values ​​between the above values;

[0014] Step 4: The melt obtained after melt mixing is extruded through an extruder, and then cooled and granulated to obtain a flame retardant reinforced PC-PBT alloy material.

[0015] Furthermore, the terminal olefinic acid ester is prepared by reacting the terminal olefinic acid and aliphatic alcohols, and the reaction ratio of the terminal olefinic acid and aliphatic alcohols is 1:1-1.5.

[0016] The synthesis method of the terminal olefinic acid ester is as follows: a dilute acid and a fatty alcohol are subjected to stirring reflux reaction in a solvent, and then extracted and separated to obtain a terminal olefinic acid ester modifier; wherein the dilute acid includes a long carbon chain terminal dilute acid such as hexyl olefinic acid and 10-undecyl olefinic acid; the fatty alcohol includes a fatty alcohol such as ethanol, propanol, and butanol; and the solvent includes an acidic solution such as concentrated sulfuric acid for catalytic reaction.

[0017] Furthermore, the reinforcing filler is alkali-free glass fiber with a diameter of 10-30 um.

[0018] Furthermore, the flame retardant is any one of a bromine-based flame retardant, a silicon-based flame retardant or a phosphorus-based flame retardant.

[0019] Furthermore, the flame retardant synergist is any one of antimony trioxide, calcium oxide containing crystal water, magnesium hydroxide and aluminum hydroxide.

[0020] Furthermore, the lubricant includes any one of pentaerythritol stearate, ethylene wax or silicone oil, or a combination of at least two of them.

[0021] Further, the toughening agent includes any one or a combination of at least two of methyl methacrylate-butadiene-styrene copolymer, maleic anhydride grafted ethylene-octene copolymer elastomer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer or methyl methacrylate-styrene-silicone copolymer.

[0022] Further, the coupling agent includes any one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent, or a combination of at least two thereof; wherein the silane coupling agent includes any one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane, or a combination of at least two thereof; and the titanate coupling agent includes isopropyl dioleyloxy (dioctylphosphoyloxy) titanate.

[0023] Furthermore, the antioxidant includes any one of a hindered phenol antioxidant, a hindered amine antioxidant, a phosphite antioxidant or a thioester antioxidant, or a combination of at least two thereof.

[0024] Further, the screw speed of the extruder is 350-700 r / min, for example, it can be 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm or 700 rpm, and specific values ​​between the above points.

[0025] The present invention also proposes an application of a flame retardant reinforced PC-PBT alloy material, wherein the flame retardant reinforced PC-PBT alloy material is applied to electric control system peripheral materials such as electric control boxes and battery module components, and thus is applied to new energy vehicles and electronic and electrical manufacturing industries.

[0026] Compared with the prior art, the advantages of the present invention are:

[0027] 1. The present invention compounds PC and PBT materials to effectively improve the mechanical properties of the PC-PBT alloy material, and further inhibits the ester exchange reaction between PC and PBT by adding a terminal olefin ester additive, thereby improving the heat resistance of the material and obtaining a flame retardant reinforced PCPBT alloy material with good mechanical properties. In the presence of a flame retardant synergist, the alloy material can obtain a reinforced PC-PBT material with good flame retardancy when only a small amount of flame retardant is used.

[0028] 2. The alloy material obtained by the method of the present invention not only has excellent mechanical properties, but also has flame retardant properties enhanced by flame retardants and flame retardant synergists, and its dielectric properties are optimized to better meet the needs of peripheral materials of the electric control system, such as electric control boxes and battery modules, and can be applied to manufacturing industries such as new energy vehicles and electronic appliances. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be further described below.

[0030] The present invention provides five embodiments of PC-PBT alloy materials and three comparative examples, which are respectively recorded as embodiments 1-5 and comparative examples 1-3.

[0031] The toughening agent used in the following examples and comparative examples includes any one or a combination of at least two of methyl methacrylate-butadiene-styrene copolymer, maleic anhydride grafted ethylene-octene copolymer elastomer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer or methyl methacrylate-styrene-silicone copolymer.

[0032] The coupling agent used in the following examples and comparative examples includes any one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent, or a combination of at least two thereof.

[0033] The silane coupling agent includes any one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane or a combination of at least two thereof;

[0034] Titanate coupling agents include isopropyl dioleyloxy (dioctylphosphooxy) titanate.

[0035] The antioxidants used in the following examples and comparative examples include any one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants or thioester antioxidants, or a combination of at least two thereof.

[0036] The lubricant used in the following examples and comparative examples includes any one of pentaerythritol stearate, ethylene wax or silicone oil, or a combination of at least two thereof.

[0037] The synergists used in the following examples and comparative examples are antimony trioxide, calcium oxide containing crystal water, magnesium hydroxide or aluminum hydroxide.

[0038] The PBT resin material used in the following examples and comparative examples has a melting point of 210° C.-230° C. and a melt index of 20-40 g / 10 min. at 250° C. and a load of 5 kg.

[0039] The reinforcing filler used in the following examples and comparative examples is alkali-free glass fiber with a diameter of 10-30 um.

[0040] The terminal olefinic acid ester used is prepared by reacting a terminal olefinic acid with an aliphatic alcohol.

[0041] Comparative Example 1 (without addition of synergist and terminal olefin ester):

[0042] A PC-PBT alloy material comprises the following components in parts by weight: 30 parts of PC, 27 parts of PBT, 30 parts of reinforcing filler (glass fiber), 0 parts of terminal olefinic acid ester, 10 parts of flame retardant, 0 parts of flame retardant synergist, 0.6 parts of toughening agent, 2 parts of coupling agent, 0.2 parts of antioxidant and 0.2 parts of lubricant.

[0043] Comparative Example 2 (without adding terminal olefin ester):

[0044] A PC-PBT alloy material comprises the following components in parts by weight: 30 parts of PC, 27 parts of PBT, 30 parts of reinforcing filler (glass fiber), 0 parts of terminal olefinic acid ester, 8 parts of flame retardant, 2 parts of flame retardant synergist, 0.6 parts of toughening agent, 2 parts of coupling agent, 0.2 parts of antioxidant and 0.2 parts of lubricant.

[0045] Comparative Example 3 (adding alkyl phosphates, without adding terminal olefin esters):

[0046] A PC-PBT alloy material comprises the following components in parts by weight: PC: 29 parts, PBT: 27 parts, reinforcing filler (glass fiber): 30 parts, alkyl phosphate: 1 part, terminal olefinic acid ester: 0 parts, flame retardant: 8 parts, flame retardant synergist: 2 parts, toughening agent: 0.6 parts, coupling agent: 2 parts, antioxidant: 0.2 parts, and lubricant: 0.2 parts.

[0047] Embodiment 1:

[0048] A PC-PBT alloy material comprises the following components in parts by weight: 29 parts of PC, 27 parts of PBT, 30 parts of reinforcing filler (glass fiber), 1 part of terminal olefinic acid ester, 10 parts of flame retardant, 0 parts of flame retardant synergist, 0.6 parts of toughening agent, 2 parts of coupling agent, 0.2 parts of antioxidant and 0.2 parts of lubricant.

[0049] Embodiment 2:

[0050] A PC-PBT alloy material comprises the following components in parts by weight: 29 parts of PC, 27 parts of PBT, 30 parts of reinforcing filler (glass fiber), 1 part of terminal olefinic acid ester, 8 parts of flame retardant, 2 parts of flame retardant synergist, 0.6 parts of toughening agent, 2 parts of coupling agent, 0.2 parts of antioxidant and 0.2 parts of lubricant.

[0051] Embodiment 3:

[0052] A PC-PBT alloy material comprises the following components in parts by weight: PC: 29.5 parts, PBT: 27 parts, reinforcing filler (glass fiber): 30 parts, terminal olefinic acid ester: 0.5 parts, flame retardant: 8 parts, flame retardant synergist: 2 parts, toughening agent: 0.6 parts, coupling agent: 2 parts, antioxidant: 0.2 parts, and lubricant: 0.2 parts.

[0053] Embodiment 4:

[0054] A PC-PBT alloy material comprises the following components in parts by weight: PC: 28 parts, PBT: 27 parts, reinforcing filler (glass fiber): 30 parts, terminal olefinic acid ester: 2 parts, flame retardant: 8 parts, flame retardant synergist: 2 parts, toughening agent: 0.6 parts, coupling agent: 2 parts, antioxidant: 0.2 parts, and lubricant: 0.2 parts.

[0055] Embodiment 5:

[0056] A PC-PBT alloy material comprises the following components in parts by weight: 29 parts of PC, 27 parts of PBT, 30 parts of reinforcing filler (glass fiber), 1 part of terminal olefinic acid ester, 5 parts of flame retardant, 5 parts of flame retardant synergist, 0.6 parts of toughening agent, 2 parts of coupling agent, 0.2 parts of antioxidant and 0.2 parts of lubricant.

[0057] The preparation method of a PC-PBT alloy material in the above Examples 1-5 and Comparative Examples 1-3 is the same, specifically as follows:

[0058] Step 1: Weigh the raw material components according to the weight ratio and pre-dry the materials at a temperature of 90°C.

[0059] Step 2: according to the weight proportions of the above embodiments or comparative examples, weigh the raw material components and add them into a high-speed mixer, and mix and stir until uniform. In this embodiment, the mixing speed is 500 rpm / min and the mixing time is 6 min;

[0060] Step 3: The mixture is put into an extruder and melt-kneaded at 255°C;

[0061] Step 4: The melt obtained after melt mixing is extruded through an extruder, and then cooled and granulated to obtain a PC-PBT alloy material.

[0062] The PC-PBT alloy materials prepared in the above comparative examples 1-3 and embodiments 1-5 were respectively subjected to tensile property test, bending property test, impact property test, heat deformation temperature test and flame retardant property test.

[0063] Among them, the test methods and standards used are as follows:

[0064] (1) Tensile properties: The elongation at break (%) and tensile strength (MPa) of the material were tested according to the method in ASTM D638;

[0065] (2) Flexural properties: The flexural modulus (MPa) and flexural strength (MPa) of the material were tested according to the method in ASTM D790;

[0066] (3) Impact performance: The notched cantilever beam impact strength of the material was tested according to the method in ASTM D256, and the test environment temperature was 23°C;

[0067] (4) Heat resistance: Test the heat deformation temperature of the material according to the method in ASTM D648;

[0068] (5) Flame retardant properties: The flame retardancy of the material was tested according to the method in UL94.

[0069] The final test results of the PC-PBT alloy materials of the above Comparative Examples 1-3 and Examples 1-5 are shown in Table 1 below:

[0070] Table 1

[0071]

[0072] From the comparison results of the performance test data of Examples 1-5 and Comparative Examples 1-3 in Table 1, it can be seen that compared with Comparative Examples 1-3, Examples 1-5 of the present invention modify the PC-PBT alloy material by adding terminal olefin esters, flame retardants, and synergists, so that the obtained material has a tensile strength of 128-135 MPa, a tensile elongation at break of 2.9-3.5%, a flexural modulus of 9000-9300 MPa, a flexural strength of 200-208 MPa, an Izod notched impact strength of 130-145 J / m, a heat deformation temperature of 130-137°C, higher impact toughness, and better mechanical properties.

[0073] In addition, from the test results of Example 1 and Comparative Example 1, it can be seen that the strength and heat deformation temperature of the material of Example 1 with the addition of terminal olefin ester are significantly improved; by comparing the test results of Example 2 and Comparative Example 3, it can be seen that compared with Comparative Example 3, the heat deformation temperature of Example 2 is significantly improved, and the strength and toughness are improved.

[0074] It can be seen that by adding terminal olefin esters to PC-PBT alloy materials, the mechanical properties and heat resistance of the composite materials can be effectively enhanced, and at the same time, the flame retardant properties of the materials can be enhanced in the presence of flame retardants and flame retardant synergists.

[0075] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any technician in the relevant technical field, without departing from the scope of the technical solution of the present invention, makes any form of equivalent replacement or modification to the technical solution and technical content disclosed in the present invention, which does not depart from the content of the technical solution of the present invention and still falls within the protection scope of the present invention.

Claims

1. A method for preparing a flame retardant reinforced PC-PBT alloy material, characterized in that: The PC-PBT alloy material is composed of the following components in parts by weight: PC: 20-60 parts, PBT: 20-60 parts, reinforcing filler: 5-50 parts, flame retardant: 5-12 parts, flame retardant synergist: 0.1-3 parts, terminal olefin ester: 0.1-2 parts, toughening agent: 0.1-2 parts, coupling agent: 0.5-5 parts, antioxidant: 0.01-5 parts, lubricant: 0.01-5 parts The preparation method of the PC-PBT alloy material comprises: Step 1: according to the weight ratio, weigh the raw material components and add them into a high-speed mixer, and mix and stir evenly; Step 2: Put the mixture into an extruder and melt-mix it at 240-270°C; Step 3: The melt obtained after melt mixing is extruded through an extruder to obtain a preparation method for a flame retardant reinforced PC-PBT alloy material.

2. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The terminal olefinic acid ester is prepared by reacting terminal olefinic acid and aliphatic alcohols, and the reaction ratio of terminal olefinic acid and aliphatic alcohols is 1:1-1.5; the synthesis method of the terminal olefinic acid ester is: stirring and refluxing the terminal dilute acid and aliphatic alcohol in a solvent, and then extracting and separating, so as to obtain a terminal dilute acid ester modifier; wherein the dilute acid includes hexanoic acid and 10-undecane dilute acid type long carbon chain terminal dilute acids; the fatty alcohol includes ethanol, propanol and butanol type fatty alcohols; the solvent includes concentrated sulfuric acid solution.

3. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The reinforcing filler is alkali-free glass fiber with a diameter of 10-30um.

4. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The flame retardant is any one of a bromine flame retardant, a silicon flame retardant or a phosphorus flame retardant.

5. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The flame retardant synergist is any one of antimony trioxide, calcium oxide containing crystal water, magnesium hydroxide and aluminum hydroxide.

6. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The lubricant includes any one of pentaerythritol stearate, ethylene wax or silicone oil, or a combination of at least two of them.

7. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The toughening agent includes any one of methyl methacrylate-butadiene-styrene copolymer, maleic anhydride grafted ethylene-octene copolymer elastomer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer or methyl methacrylate-styrene-silicone copolymer or a combination of at least two thereof.

8. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The coupling agent includes any one of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent, or a combination of at least two of them.

9. The method for preparing the flame retardant reinforced PC-PBT alloy material according to claim 1, characterized in that: The antioxidant includes any one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants or thioester antioxidants, or a combination of at least two of them.

10. An application of the flame retardant reinforced PC-PBT alloy material according to any one of claims 1 to 9, characterized in that: The flame retardant reinforced PC-PBT alloy material is applied to electric control system peripheral materials such as electric control boxes and battery module parts, and thus is applied to new energy vehicles and electronic and electrical manufacturing industries.

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