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

Abstract

This invention proposes a preparation method and application of a flame-retardant reinforced PC-PBT alloy material. 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 acrylate: 0.1-2 parts, toughening agent: 0.1-2 parts, coupling agent: 0.5-5 parts, antioxidant: 0.01-5 parts, and lubricant: 0.01-5 parts. The preparation method includes: weighing the raw material components according to the weight ratio and adding them to a high-speed mixer for uniform mixing; feeding the mixture into an extruder for melt mixing; and extruding the resulting melt through an extruder to obtain the flame-retardant reinforced PC-PBT alloy material. This invention combines PC and PBT materials and further inhibits the transesterification reaction of PC and PBT through a terminal acrylate additive to obtain a flame-retardant reinforced PCPBT alloy material with good mechanical properties. This material can meet the needs of peripheral materials for electronic control systems, such as control boxes and battery modules, and can be applied in the manufacturing industries of new energy vehicles and electronic appliances.

Description

Technical Field

[0001] This invention relates to the field of polymer material modification technology, and in particular to a method for preparing and applying a low flame retardant reinforced PC-PBT alloy material. Background Technology

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

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

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

[0005] The purpose of this invention is to propose a method for preparing flame-retardant reinforced PC-PBT alloy materials that can effectively inhibit transesterification reactions and have excellent mechanical properties.

[0006] To achieve the above objectives, this invention proposes 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 acrylate: 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 includes:

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

[0010] Step 2: Add the dried raw materials to a high-speed mixer and mix thoroughly.

[0011] Preferably, the mixing 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, it can be 4 min, 5 min, 6 min, 8 min, 10 min, 12 min or 14 min, as well as specific values ​​between the above-mentioned time points.

[0013] Step 3: Feed the mixture into an extruder and melt-blend it at 240-270℃. The melting-blending temperature can be 245℃, 250℃, 255℃, 260℃, 265℃, or specific values ​​between the above points.

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

[0015] Furthermore, the terminal acrylate is prepared by reacting terminal acrylate with aliphatic alcohol, wherein the reaction ratio of terminal acrylate to aliphatic alcohol is 1:1-1.5.

[0016] The method for synthesizing the terminal olefin ester is as follows: an olefinic acid and a fatty alcohol are reacted under stirring and reflux in a solvent, followed by extraction and separation to obtain a terminal olefin ester modifier; wherein the olefinic acid includes long-chain terminal olefinic acids such as hexenoic acid and 10-undecenoic acid; the fatty alcohol includes fatty alcohols 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 μm.

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

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

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

[0021] Furthermore, the toughening agent includes any one or a combination of at least two of the following: 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] Furthermore, the coupling agent includes any one or a combination of at least two of silane coupling agents, titanate coupling agents, or aluminate coupling agents; wherein the silane coupling agent includes any one or a combination of at least two of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-glycidoxypropyltriethoxysilane; and the titanate coupling agent includes isopropyl dioleoyloxy(dioctylphosphoxy) titanate.

[0023] Furthermore, the antioxidant includes any one or a combination of at least two of the following: hindered phenolic antioxidants, hindered amine antioxidants, phosphite antioxidants, or thioester antioxidants.

[0024] Furthermore, the extruder screw speed 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] This invention also proposes an application of a flame-retardant reinforced PC-PBT alloy material, which is used in peripheral materials of electronic control systems, such as electronic control boxes and battery module components, thereby being applied to the new energy vehicle and electronics manufacturing industries.

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

[0027] 1. This invention combines PC and PBT materials to effectively improve the mechanical properties of the PC-PBT alloy material. Furthermore, by adding terminal acrylate additives, the transesterification reaction between PC and PBT is further inhibited, improving the heat resistance of the material and obtaining a flame-retardant reinforced PC-PBT alloy material with good mechanical properties. In the presence of flame retardant synergists, this alloy material can achieve good flame retardancy with only a small amount of flame retardant.

[0028] 2. The alloy material obtained by the method of this invention not only has excellent mechanical properties, but also enhances the flame retardant properties of the material and optimizes its dielectric properties by regulating and enhancing the flame retardant properties through flame retardants and flame retardant synergists, so as to better meet the needs of peripheral materials of electronic control systems, such as control boxes and battery modules, and can be applied in the manufacturing industries of new energy vehicles, electronics and electrical appliances, etc. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be further described below.

[0030] This invention proposes five embodiments of PC-PBT alloy materials and three comparative examples, referred to as Examples 1-5 and Comparative Examples 1-3, respectively.

[0031] The toughening agents used in the following examples and comparative examples include any one or a combination of at least two of the following: 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 agents used in the following examples and comparative examples include any one or a combination of at least two of silane coupling agents, titanate coupling agents, or aluminate coupling agents.

[0033] The silane coupling agent includes any one or a combination of at least two of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-glycidoxypropyltriethoxysilane.

[0034] Titanate coupling agents include isopropyl dioleoyloxy (dioctylphosphono) titanate.

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

[0036] The lubricants used in the following examples and comparative examples include any one or a combination of at least two of pentaerythritol stearate, vinyl wax, or silicone oil.

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

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

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

[0040] The terminal acrylate used is prepared by reacting terminal acrylate with aliphatic alcohols.

[0041] Comparative Example 1 (without synergist and terminal acrylate):

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

[0043] Comparative Example 2 (without terminal acrylate):

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

[0045] Comparative Example 3 (with added alkyl phosphates, but without terminal acrylates):

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

[0047] Example 1:

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

[0049] Example 2:

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

[0051] Example 3:

[0052] A PC-PBT alloy material, by weight, comprises the following components: PC: 29.5 parts, PBT: 27 parts, reinforcing filler (glass fiber): 30 parts, terminal acrylate: 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, lubricant: 0.2 parts.

[0053] Example 4:

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

[0055] Example 5:

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

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

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

[0059] Step 2: Weigh the raw material components according to the weight ratio of each embodiment or comparative example above and add them to the high-speed mixer. 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: Feed the mixture into an extruder and melt-mix it at 255°C;

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

[0062] The PC-PBT alloy materials obtained in Comparative Examples 1-3 and Examples 1-5 were subjected to tensile property tests, bending property tests, impact property tests, heat distortion temperature tests, and flame retardant property tests, respectively.

[0063] The testing 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) Bending properties: The bending modulus (MPa) and bending strength (MPa) of the material were tested according to the method in ASTM D790;

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

[0067] (4) Heat resistance: The heat distortion temperature of the material shall be tested according to the method in ASTM D648;

[0068] (5) Flame retardancy: The flame retardancy of the material shall be tested in accordance with the method in UL94.

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

[0070] Table 1

[0071]

[0072] As can be seen from the comparison of the performance test data of Examples 1-5 and Comparative Examples 1-3 in Table 1, compared with Comparative Examples 1-3, Examples 1-5 of the present invention modify the PC-PBT alloy material by adding terminal acrylate, flame retardant and synergist, resulting in a tensile strength of 128-135MPa, tensile elongation at break of 2.9-3.5%, flexural modulus of 9000-9300MPa, flexural strength of 200-208MPa, cantilever beam notched impact strength of 130-145J / m, heat distortion temperature of 130-137℃, higher impact toughness and better mechanical properties.

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

[0074] Therefore, it can be seen that by adding terminal acrylate to PC-PBT alloy materials, the mechanical properties and heat resistance of the composite material can be effectively enhanced, and the flame retardant properties of the material can be enhanced in the presence of flame retardants and flame retardant synergists.

[0075] The above are merely preferred embodiments of the present invention and do not constitute any limitation on the present invention. Any equivalent substitutions or modifications made by those skilled in the art to the technical solutions and content disclosed in the present invention without departing from the scope of the present invention shall be deemed to have remained 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 acrylate: 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 includes: Step 1: Weigh the raw material components according to the stated weight ratio and add them to the high-speed mixer, then mix and stir evenly; Step 2: Feed the mixture into an extruder and melt-blend it at 240-270℃; Step 3: The melt obtained after melt mixing is extruded through an extruder to obtain flame-retardant reinforced PC-PBT alloy material; The terminal olefin ester is prepared by reacting a terminal olefinic acid with an aliphatic alcohol, wherein the reaction ratio of the terminal olefinic acid to the aliphatic alcohol is 1:1-1.

5. The synthesis method of the terminal olefin ester is as follows: the terminal olefinic acid and the fatty alcohol are reacted under stirring and reflux in a solvent, followed by extraction and separation to obtain the terminal olefin ester modifier; wherein the olefinic acid includes hexenoic acid and 10-undecenoic acid; the fatty alcohol includes ethanol, propanol and butanol fatty alcohols; and the solvent includes concentrated sulfuric acid solution.

2. 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 10-30 μm.

3. 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 bromine-based flame retardants, silicon-based flame retardants, or phosphorus-based flame retardants.

4. 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 water of crystallization, magnesium hydroxide, and aluminum hydroxide.

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

6. 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 or a combination of at least two of the following: 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.

7. 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 or a combination of at least two of silane coupling agents, titanate coupling agents, or aluminate coupling agents.

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

9. An application of the flame-retardant reinforced PC-PBT alloy material as described in any one of claims 1-8, characterized in that, The flame-retardant reinforced PC-PBT alloy material is used in peripheral materials of electronic control systems, such as control boxes and battery module components, and is thus applied in the new energy vehicle and electronics manufacturing industries.

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