High-strength flame-retardant PCABS material and preparation method thereof

Abstract

The invention relates to a high-strength flame-retardant PCABS (Polycarbonate Acrylonitrile Butadiene Styrene) material and a preparation method thereof. The high-strength flame-retardant PCABS material comprises the following components in parts by mass: 80-100 parts of PC resin, 10-20 parts of ABS resin, 5-10 parts of modified carbon nanotubes, 5-10 parts of polyurethane ether, 10-15 parts of a flame retardant and 5-10 parts of an auxiliary agent, wherein the modified carbon nano tube is a carbon nano tube of which the surface is coated with polyurethane ether. According to the invention, the modified carbon nanotubes are compounded with substances such as PC and ABS resin, so that the affinity among various components is effectively improved, and the defect of insufficient strength of PCAB is overcome, so that the product has good electrical properties, flame retardancy and better stability and mechanical properties, solves the problems in the prior art, and has a good application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of polymer composite materials, in particular to a high-strength flame-retardant PCABS material and a preparation method thereof. Background Art

[0002] PCABS composite material is a thermoplastic plastic made by fusing PC (polycarbonate) and ABS (acrylonitrile-butadiene-styrene polymer). It combines the heat resistance and stability of PC material with the good processability of ABS material. It has excellent properties and a wide range of uses. It has been widely used in many key industries such as electronics, electrical, communications, and automobiles.

[0003] In existing PCABS composite material applications, various functional additives are often added according to specific application scenarios, such as toughness enhancers, thermal conductivity additives, fire retardants, and dielectric regulators.

[0004] Flame-retardant PCABS materials can usually reach UL94 V0 or even higher flame retardancy by adding efficient flame retardants. They can quickly extinguish themselves after being ignited, and will not cause the fire to spread, effectively reducing the risk of fire. However, in flame-retardant PCABS materials, there may be insufficient compatibility between flame retardants and organic polymers and other components. After mixing multiple components, agglomeration and uneven dispersion will occur, thus weakening the structural stability and mechanical properties of the composite material. For example, after fasteners such as screws are installed, if they are left for a period of time, cracking will occur as stress is released; and the surface defects and reduced mechanical strength caused by the insufficient toughness of the material itself and the insufficient polymerization of the flame retardant even affect the flame retardant properties of the material itself. Directly adding toughening materials such as glass fiber and calcium sulfate whiskers will further reduce the compatibility of the mixture, making it difficult to achieve the desired improvement effect.

[0005] Therefore, how to ensure the flame retardant properties of flame retardant PCABS materials while giving them stronger mechanical properties such as bending strength and tensile strength is a difficult problem faced in this field.

[0006] In summary, it is urgent to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0007] Based on this, the present invention has developed a high-strength flame-retardant PCABS material and a preparation method thereof. The present invention uses modified carbon nanotubes to compound with PC, ABS resin and other materials, effectively improving the affinity between multiple components, overcoming the defect of insufficient strength of PCAB, giving the material stronger electrical properties, while making the product have good flame retardant properties and better stability and mechanical properties, solving the problems in the prior art and having good application prospects.

[0008] One object of the present invention is to provide a high-strength flame-retardant PCABS material, wherein the high-strength flame-retardant PCABS material comprises the following components in parts by mass:

[0009]

[0010]

[0011] in,

[0012] The modified carbon nanotubes are carbon nanotubes with polyamine ether coated on the surface.

[0013] Furthermore, the raw material of the carbon nanotubes is carboxylated carbon nanotubes.

[0014] Furthermore, the auxiliary agent is selected from one or more of an anti-dripping agent, a toughening agent, an antioxidant, a lubricant, and an anti-ultraviolet agent.

[0015] Another object of the present invention is to provide a method for preparing the above-mentioned high-strength flame-retardant PCABS material, wherein the method for preparing the high-strength flame-retardant PCABS material comprises the following steps:

[0016] Preparation of modified carbon nanotubes:

[0017] S1, mixing carboxylated carbon nanotubes, epoxy resin and TPP (triphenylphosphine), and ultrasonicating;

[0018] S2, heating the reaction, then adding ethanolamine and propylene glycol methyl ether, and continuing the reaction under the protection of inert gas;

[0019] S3, add propylene glycol methyl ether, continue the reaction, and obtain the product.

[0020] Furthermore, the mass ratio of the carboxylated carbon nanotubes to the epoxy resin is 1:20-40.

[0021] Furthermore, in step S2, the temperature of the heating reaction is 80-90°C, and the temperature of the continued reaction is 120-140°C.

[0022] Furthermore, the mass of the propylene glycol methyl ether is 30-50 times that of the carboxymethyl carbon nanotubes.

[0023] Furthermore, it also includes:

[0024] PC resin, ABS resin, modified carbon nanotubes, polyamine ether, flame retardant and additives are mixed, added into an extruder, melt-extruded and granulated at 230-250° C. to obtain a high-strength flame-retardant PCABS material.

[0025] The present invention has the following beneficial effects:

[0026] The present invention provides a high-strength flame-retardant PCABS material and a preparation method thereof. The present invention obtains the PCABS material by compounding polyamine ether modified carbon nanotubes with PC resin, ABS resin and other components. The modified carbon nanotubes first react with epoxy resin and carboxylated carbon nanotubes to introduce groups such as benzene rings and epoxy groups into the surface of the carbon nanotubes, and then further react with ethanolamine to form a polyamine ether-bisphenol resin coated structure on the surface of the modified carbon nanotubes. The addition of carbon nanotubes effectively improves the electrical properties of PCABS materials, and can meet the requirements for conductive materials and antistatic materials. Moreover, the modified carbon nanotubes, on the one hand, have similar benzene rings, amino groups, ether bonds and other groups as PC resins and ABS resins, and the surface is more regular, which significantly improves the compatibility between carbon nanotubes and organic resins, and is beneficial to increase the dispersion effect of components and improve the stability of composite materials; on the other hand, the active groups on the surface of the modified carbon nanotubes can form chemical crosslinks and intermolecular forces with the active groups in components such as resins, thereby forming a more stable three-dimensional structure, further exerting the toughening effect of carbon fibers, and improving the bending and tensile strength of the product; in addition, the modified carbon nanotubes can adsorb and bind flame retardants containing benzene and ether groups through the surface polyamine ether structure. Therefore, under the synergistic effect of multiple components, not only the flame retardant ability of PCABS materials is guaranteed, but also the mechanical strength of the product is greatly improved, which can meet a wider range of application needs and is of great significance to the development of this field. DETAILED DESCRIPTION

[0027] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0028] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0029] It should be understood that, except in any operating examples, or otherwise indicated, the amounts of ingredients used in the specification or all numbers, for example, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification are approximate values ​​that vary according to the desired properties to be obtained by the present invention.

[0030] The grade of PC resin in the embodiment of the present invention is PC IR2200.

[0031] The ABS resin grade in the embodiment of the present invention is ABS275.

[0032] The particle size of the carbon nanotubes in the embodiment of the present invention is 20 nm.

[0033] The preparation method of the polyamine ether in the embodiment of the present invention comprises the following steps:

[0034] Bisphenol A glycidyl ether and ethanolamine in a molar ratio of 1:0.9 are mixed, stirred, degassed, reacted at 100° C. for 3 h, then treated at 120° C. for 0.5 h, and granulated to obtain polyamine ether.

[0035] The flame retardant in the embodiment of the present invention is PX-220 hydroquinone bis(diphenyl phosphate) halogen-free flame retardant, purchased from Dongguan Xingyuan Chemical Co., Ltd.

[0036] The additives in the embodiment of the present invention are anti-dripping agent PTFE DB154, toughening agent MBS2620, and antioxidant 1010 in a mass ratio of 1:8:1.

[0037] The "parts" in the embodiments of the present invention refer to parts by mass.

[0038] The method for preparing carboxylated carbon nanotubes in the embodiment of the present invention comprises the following steps:

[0039] The carbon nanotubes were immersed in nitric acid with a mass concentration of 60%, ultrasonically dispersed for 0.5 h, then refluxed at 120° C. for 24 h, and then filtered, washed, and dried to obtain carboxylated carbon nanotubes.

[0040] Example 1

[0041] A high-strength flame-retardant PCABS material, comprising the following components in parts by mass:

[0042]

[0043] The preparation method of the high-strength flame-retardant PCABS material comprises the following steps:

[0044] S1, blending carboxylated carbon nanotubes, E-51 epoxy resin and TPP in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 h;

[0045] S2, then react at 85°C for 24h, then add ethanolamine and propylene glycol methyl ether in a mass ratio of 1:4.8 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and continue to react at 140°C for 3h under nitrogen protection;

[0046] S3, then add propylene glycol methyl ether in an amount equal to that of S2, react at 140°C for 3h, extract, wash with propylene glycol methyl ether, and dry to obtain a product;

[0047] S4. According to the above mass fractions, PC resin, ABS resin, modified carbon nanotubes, polyamine ether, flame retardant and additives are mixed, added into an extruder, melt-extruded and granulated at 230-250°C to obtain a high-strength flame-retardant PCABS material.

[0048] Example 2

[0049] A high-strength flame-retardant PCABS material, comprising the following components in parts by mass:

[0050]

[0051] The preparation method of the high-strength flame-retardant PCABS material comprises the following steps:

[0052] S1, blending carboxylated carbon nanotubes, E-51 epoxy resin and TPP in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 h;

[0053] S2, then react at 85°C for 24h, then add ethanolamine and propylene glycol methyl ether in a mass ratio of 1:4.8 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and continue to react at 140°C for 3h under nitrogen protection;

[0054] S3, then add propylene glycol methyl ether in an amount equal to that of S2, react at 140°C for 3h, extract, wash with propylene glycol methyl ether, and dry to obtain a product;

[0055] S4. According to the above mass fractions, PC resin, ABS resin, modified carbon nanotubes, polyamine ether, flame retardant and additives are mixed, added into an extruder, melt-extruded and granulated at 230-250°C to obtain a high-strength flame-retardant PCABS material.

[0056] Example 3

[0057] A high-strength flame-retardant PCABS material, comprising the following components in parts by mass:

[0058]

[0059] The preparation method of the high-strength flame-retardant PCABS material comprises the following steps:

[0060] S1, blending carboxylated carbon nanotubes, E-51 epoxy resin and TPP in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 h;

[0061] S2, then react at 85°C for 24h, then add ethanolamine and propylene glycol methyl ether in a mass ratio of 1:4.8 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and continue to react at 140°C for 3h under nitrogen protection;

[0062] S3, then add propylene glycol methyl ether in an amount equal to that of S2, react at 140°C for 3h, extract, wash with propylene glycol methyl ether, and dry to obtain a product;

[0063] S4. According to the above mass fractions, PC resin, ABS resin, modified carbon nanotubes, polyamine ether, flame retardant and additives are mixed, added into an extruder, melt-extruded and granulated at 230-250°C to obtain a high-strength flame-retardant PCABS material.

[0064] Comparative Example 1

[0065] A PCABS material. The difference between this comparative example and Example 1 is that the modified carbon nanotubes are replaced by a mixture of carboxylated carbon nanotubes and polyamine ether in a mass ratio of 2:1. Other ingredients and preparation methods are the same as those in Example 1.

[0066] Comparative Example 2

[0067] A PCABS material, the difference between this comparative example and Example 1 is that: the modified carbon nanotubes are replaced by carbon nanotubes modified by an epoxysilane coupling agent: the carbon nanotubes are immersed in a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, reacted at 120°C for 5 hours, washed and dried to obtain hydroxylated carbon nanotubes; then, a mixed solution of ethanol and water in a volume ratio of 9:1 is used as a solvent, hydroxylated carbon nanotubes and KH560 in a mass ratio of 2:1 are added, reacted at 80°C for 10 hours, washed and dried to obtain a product, and other components and preparation methods are the same as those in Example 1.

[0068] Test Case

[0069] Test method:

[0070] The PCABS materials prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests, and the flame retardancy was tested according to UL-94, and the tensile strength, flexural strength, and notched impact strength were measured according to ISO 527, ISO 178, ISO 179, and other standards.

[0071] The test results are shown in Table 1.

[0072] Table 1 Performance test results

[0073] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Surface resistance(Ω) <![CDATA[1×10 7 ]]> <![CDATA[1×10 7 ]]> <![CDATA[1×10 7 ]]> <![CDATA[1×10 7 ]]> <![CDATA[1×10 7 ]]> Flame retardant V0 V0 V0 V1 V1 Tensile strength(MPa) 65 68 70 51 56 Bending strength(MPa) 87 90 96 72 80 <![CDATA[Notched impact strength (KJ / m 2 )]]> 43 45 46 33 38

[0074] According to Table 1, it can be concluded that the high-strength flame-retardant PCABS materials prepared in Examples 1-3 have excellent flame-retardant and electrical properties, and the tensile strength, bending strength and notched impact strength are significantly better than those of the comparative examples. Comparative Example 1 replaces the modified carbon nanotubes with a mixture of carbon nanotubes and polyamine ethers, which cannot improve the compatibility between the components, and it is difficult to form adsorption and bonding between the components, resulting in a significant decrease in the stability, mechanical strength and flame-retardant properties of the material; while Comparative Example 2 uses a silane coupling agent to modify the carbon nanotubes. Although the affinity between the components is increased, the degree of improvement is low, and the regularity of the carbon nanotube surface, the types and quantities of the introduced functional groups are all significantly different from those of the embodiments, so it is difficult to achieve a synergistic effect between the components, and the performance improvement of the composite material is not ideal. In summary, the high-strength flame-retardant PCABS material of the present invention overcomes the defects existing in the prior art and has good application prospects.

[0075] It is obvious to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered as exemplary and non-restrictive in all respects.

[0076] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A high-strength flame-retardant PCABS material, characterized in that: The high-strength flame-retardant PCABS material comprises the following components in parts by mass: in, The modified carbon nanotubes are carbon nanotubes with polyamine ether coated on the surface.

2. The high-strength flame-retardant PCABS material according to claim 1, characterized in that: The raw material of the carbon nanotubes is carboxylated carbon nanotubes.

3. The high-strength flame-retardant PCABS material according to claim 1, characterized in that: The auxiliary agent is selected from one or more of an anti-dripping agent, a toughening agent, an antioxidant, a lubricant, and an anti-ultraviolet agent.

4. The method for preparing the high-strength flame-retardant PCABS material according to any one of claims 1 to 3, characterized in that: The preparation method of the high-strength flame-retardant PCABS material comprises the following steps: Preparation of modified carbon nanotubes: S1, blending carboxylated carbon nanotubes, epoxy resin and TPP, and sonicating; S2, heating the reaction, then adding ethanolamine and propylene glycol methyl ether, and continuing the reaction under the protection of inert gas; S3, add propylene glycol methyl ether, continue the reaction, and obtain the product.

5. The method for preparing the high-strength flame-retardant PCABS material according to claim 4, characterized in that: The mass ratio of the carboxylated carbon nanotubes to the epoxy resin is 1:20-40.

6. The method for preparing the high-strength flame-retardant PCABS material according to claim 4, characterized in that: In step S2, the temperature of the heating reaction is 80-90°C, and the temperature of the continued reaction is 120-140°C.

7. The method for preparing the high-strength flame-retardant PCABS material according to claim 4, characterized in that: The mass of the propylene glycol methyl ether is 30-50 times that of the carboxymethyl carbon nanotubes.

8. The method for preparing the high-strength flame-retardant PCABS material according to claim 4, characterized in that: Also includes: PC resin, ABS resin, modified carbon nanotubes, polyamine ether, flame retardant and additives are mixed, added into an extruder, melt-extruded and granulated at 230-250° C. to obtain a high-strength flame-retardant PCABS material.

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