Environment-friendly flame-retardant high-temperature-resistant polycarbonate modified material as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly flame-retardant high-temperature-resistant polycarbonate modified material and a preparation method and application thereof, and belongs to the technical field of polycarbonate materials, the environment-friendly flame-retardant high-temperature-resistant polycarbonate modified material comprises the following raw materials by weight: 80-100 parts of polycarbonate resin, 8-16 parts of a flame retardant, 12-20 parts of a high-temperature-resistant filler, 1-2 parts of a coupling agent, and 2-3 parts of a lubricant; the polycarbonate resin, the flame retardant and the high-temperature-resistant filler are dried and then mixed with the coupling agent and the lubricant, the mixture is added into a double-screw extruder, and extrusion, traction, granulation and drying are performed to obtain the flame-retardant polycarbonate composite material. By adding the flame retardant, not only can the polycarbonate material be endowed with efficient and environment-friendly flame retardant property, but also the interaction between the flame retardant and the material components can be improved, and the durability of the flame retardant property is improved; by introducing the high-temperature-resistant filler, the high-temperature resistance of the polycarbonate material can be effectively improved; the obtained polycarbonate modified material can be subjected to injection molding to form various injection molded parts for outdoor use, and is applied to the fields of telecommunication, IT, automobiles and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of polycarbonate materials, and in particular, relates to an environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material, a preparation method thereof, and an application thereof. Background Art

[0002] Polycarbonate (PC) has excellent light transmittance, impact toughness, dimensional stability and certain flame retardancy. It is widely used in electronics, electrical appliances, aerospace, automobile and other industries.

[0003] With the increasing development of various industries, the requirements for the flame retardant properties of polycarbonate are becoming more and more stringent. PC will produce a large amount of dripping and smoke during the combustion process, causing serious harm. Therefore, to meet the requirements of high flame retardant properties and further improve its flame retardant properties to adapt to the use requirements of different fields is the current research focus.

[0004] Usually, adding flame retardants is used to improve the flame retardant properties of polymers. However, the addition of some flame retardants will not only affect the performance of the material, but also produce toxic and harmful substances during the combustion process, causing environmental pollution. Although some compound flame retardant systems can effectively improve the flame retardancy of the material, the compatibility of each component with the substrate and the compatibility of each component are poor, which seriously affects the comprehensive performance of the composite material. In addition, the additional flame retardant will gradually migrate and seep out over time, making it difficult to ensure the durability of the flame retardant performance. Summary of the invention

[0005] The purpose of the present invention is to provide an environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material, and a preparation method and application thereof. By adding a homemade flame retardant, not only can the polycarbonate material be endowed with efficient and environmentally friendly flame retardant properties, but also the interaction between the flame retardant and the material components can be enhanced, thereby improving the durability of the flame retardant properties; by introducing a high-temperature resistant filler, the high-temperature resistance of the polycarbonate material can be effectively improved; the obtained polycarbonate modified material can be injection molded into various injection molded parts for outdoor use, and is applied to the fields of telecommunications, IT, and automobiles.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] An environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material comprises the following raw materials in parts by weight:

[0008] 80-100 parts of polycarbonate resin, 8-16 parts of flame retardant, 12-20 parts of high temperature resistant filler, 1-2 parts of coupling agent, 2-3 parts of lubricant;

[0009] The preparation method of the polycarbonate modified material is:

[0010] The polycarbonate resin, flame retardant and high temperature resistant filler are dried at 120°C for 5-6 hours, then the three, coupling agent and lubricant are mixed evenly according to a proportion, added into a twin-screw extruder, extruded, pulled, granulated and dried at 220°C-280°C to prepare the polycarbonate modified material.

[0011] Furthermore, the high temperature resistant filler is a mixture of one or more of quartz powder, silicon powder, mica powder and talcum powder in any proportion.

[0012] Furthermore, the coupling agent is silane coupling agent KH560.

[0013] Under the coupling effect of silane coupling agent KH560, the uniform distribution of high temperature resistant fillers in polycarbonate resin can be promoted. The high temperature resistant fillers can not only increase the mechanical properties of polycarbonate materials, but also effectively improve the high temperature resistance of polycarbonate materials due to their own high temperature resistance.

[0014] Furthermore, the lubricant is pentaerythritol stearate.

[0015] Furthermore, the flame retardant is prepared by the following steps:

[0016] (1) Add p-phenylenediamine, sodium bicarbonate and ethanol to a dry three-necked flask, place the flask in an ice bath, stir and mix, and when the system temperature stabilizes at 0-2°C, slowly drop 1-chlorohexadecane under stirring. After the dropwise addition is complete, react at 0-2°C for 3 hours, and remove the solvent by rotary evaporation under reduced pressure to obtain intermediate 1;

[0017] The ratio of p-phenylenediamine, sodium bicarbonate and 1-chlorohexadecane is 0.1 mol:8.4 g:0.1 mol;

[0018] Under the action of sodium bicarbonate, -NH2 on p-phenylenediamine reacts with 1-chlorohexadecane to undergo a nucleophilic substitution reaction to obtain intermediate 1. The process is as follows:

[0019]

[0020] (2) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, intermediate 1, sodium methoxide, methanol and 1,4-dioxane were added, and refluxed at 65° C. for 6 h. After the reaction was completed, rotary evaporation was performed to remove methanol and 1,4-dioxane in the system to obtain intermediate 2;

[0021] The ratio of the amount of intermediate 1 to sodium methoxide is 15 g:5.4 g;

[0022] The -NH2 on intermediate 1 reacts with sodium methoxide to form a salt, namely intermediate 2. The process is as follows:

[0023]

[0024] (3) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, add intermediate 2 and 1,4-dioxane, stir for 20-30 minutes, introduce nitrogen for 8-10 minutes to replace the oxygen in the flask, and then add phosphorus oxychloride, control the temperature during the addition not to exceed 30° C., stir at a low speed for 30 minutes, then increase the stirring speed and raise the temperature, react at 85° C. for 6 hours, and after the reaction is complete, filter and separate to obtain the product, wash with water, and dry to obtain a flame retardant;

[0025] The ratio of the amount of intermediate 2 and phosphorus oxychloride is 17.2g:5.1g;

[0026] Intermediate 2 reacts with phosphorus oxychloride as shown below to obtain a flame retardant:

[0027]

[0028] From the molecular structure point of view, the prepared flame retardant contains PN synergistic flame retardant components, benzene rings, 16 C alkyl long chains and -NH- functional groups. Specifically, the PN synergistic flame retardant components have the combined advantages of P-series and N-series flame retardants, and are safe and environmentally friendly, so that the flame retardant has efficient and environmentally friendly flame retardant properties; the presence of the benzene ring can not only improve the rigidity of the flame retardant itself, but also improve the compatibility with the polycarbonate resin chain and promote the dispersion of the flame retardant; the 16 C alkyl long chain has extremely high flexibility and can be inserted between the polycarbonate chains, which plays a role in toughening and improving the physical interaction between the flame retardant and the polycarbonate; the -NH- functional group and the epoxy group on the coupling agent KH560 have high reactivity, that is, a stronger interaction is generated between the flame retardant, the coupling agent and the filler, which complements the above-mentioned effects, thereby improving the defects of easy migration and exudation of the flame retardant and obtaining a relatively stable flame retardant property.

[0029] It should be noted that the flame retardant also contains aniline in its molecular structure. Aniline is an excellent anti-aging agent. Therefore, while avoiding the additional addition of an anti-aging agent, the addition of the flame retardant can also improve the anti-aging performance of the polycarbonate material to a certain extent.

[0030] Another object of the present invention is to provide the above-mentioned polycarbonate modified material which can be injection molded into various injection molded parts for outdoor use, and applied to the fields of telecommunications, IT and automobiles.

[0031] Beneficial effects of the present invention:

[0032] The invention not only can endow the polycarbonate material with efficient and environmentally friendly flame retardant properties by adding a self-made flame retardant, but also can enhance the interaction between the flame retardant and the material components, thereby improving the durability of the flame retardant properties; by introducing a high temperature resistant filler, the high temperature resistance of the polycarbonate material can be effectively enhanced; the obtained polycarbonate modified material can be injection molded into various injection molded parts for outdoor use, and can be applied to the fields of telecommunications, IT, and automobiles. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] The flame retardant is prepared by the following steps:

[0036] (1) Add 0.1 mol of p-phenylenediamine, 8.4 g of sodium bicarbonate and 60 mL of ethanol to a dry three-necked flask, place the flask in an ice bath, stir and mix, and when the system temperature stabilizes at 0-2°C, slowly drop 0.1 mol of 1-chlorohexadecane under stirring. After the dropwise addition is complete, react at 0-2°C for 3 hours, and remove the solvent by vacuum rotary evaporation to obtain intermediate 1;

[0037] (2) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 15 g of intermediate 1, 5.4 g of sodium methoxide, 20 mL of methanol and 60 mL of 1,4-dioxane were added, and the mixture was refluxed at 65° C. for 6 h. After the reaction was completed, a rotary evaporation was performed to remove methanol and 1,4-dioxane in the system to obtain intermediate 2;

[0038] (3) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, add 17.2 g of intermediate 2 and 100 mL of 1,4-dioxane, stir for 25 min, introduce nitrogen for 10 min to replace the oxygen in the flask, then add 5.1 g of phosphorus oxychloride, control the temperature during the addition not to exceed 30° C., stir at a low speed for 30 min, then increase the stirring speed and raise the temperature, react at 85° C. for 6 h, and after the reaction is complete, filter and separate to obtain the product, wash with water, and dry to obtain a flame retardant;

[0039] Example 2

[0040] An environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material comprises the following raw materials in parts by weight:

[0041] 80 parts of polycarbonate resin, 8 parts of flame retardant, 12 parts of quartz powder, 1 part of silane coupling agent KH560, 2 parts of pentaerythritol stearate;

[0042] The preparation method of the polycarbonate modified material is:

[0043] The polycarbonate resin, flame retardant and quartz powder are dried at 120° C. for 5 hours, and then the three, silane coupling agent KH560 and pentaerythritol stearate are mixed evenly according to a proportion, added into a twin-screw extruder, and extruded, pulled, granulated and dried at 220° C. to prepare the polycarbonate modified material.

[0044] Example 3

[0045] An environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material comprises the following raw materials in parts by weight:

[0046] 90 parts of polycarbonate resin, 12 parts of flame retardant, 16 parts of silicon powder, 1.5 parts of silane coupling agent KH560, 2.5 parts of pentaerythritol stearate;

[0047] The preparation method of the polycarbonate modified material is:

[0048] The polycarbonate resin, flame retardant and silicon powder are dried at 120° C. for 5.5 hours, and then the three, silane coupling agent KH560 and pentaerythritol stearate are mixed evenly in proportion, added into a twin-screw extruder, and extruded, pulled, granulated and dried at 250° C. to prepare the polycarbonate modified material.

[0049] Example 4

[0050] An environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material comprises the following raw materials in parts by weight:

[0051] 100 parts of polycarbonate resin, 16 parts of flame retardant, 20 parts of mica powder, 2 parts of silane coupling agent KH560, 3 parts of pentaerythritol stearate;

[0052] The preparation method of the polycarbonate modified material is:

[0053] The polycarbonate resin, flame retardant and mica powder are dried at 120° C. for 6 hours, then the three, silane coupling agent KH560 and pentaerythritol stearate are mixed evenly in proportion, added into a twin-screw extruder, and extruded, pulled, granulated and dried at 280° C. to prepare the polycarbonate modified material.

[0054] Comparative Example 1

[0055] The flame retardant in Example 2 was replaced with polyphosphate melamine of the same mass, and the other raw materials and preparation process remained unchanged.

[0056] Comparative Example 2

[0057] The flame retardant raw material in Example 2 was removed, and the other raw materials and preparation process remained unchanged.

[0058] Comparative Example 3

[0059] PC resin.

[0060] The weight average molecular weight of the polycarbonate resin in the above examples is 32,000 and is produced by LG Chemical.

[0061] The polycarbonate materials obtained in Examples 2-4 and Comparative Examples 1-3 were processed into test specimens, and their performance was tested in the following manner:

[0062] Test tensile strength and elongation at break according to GB / T 1040.1-2018;

[0063] Impact strength was tested according to GB / T 1843-2008;

[0064] Test heat distortion temperature (1.82MPa) according to ASTM D648;

[0065] Test the flame retardant grade of materials according to UL94;

[0066] The measured results are shown in the following table:

[0067] Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Tensile strength / MPa 67.4 68.5 69.5 67.0 66.8 62.3 Elongation at break / % 119 116 114 98 101 124 <![CDATA[Impact strength / kJ·m -2 > 61.3 61.0 60.8 57.3 57.6 62.5 Heat deformation temperature / ℃ 132 134 135 131 131 126 Flame retardant grade (2mm) V-0 V-0 V-0 V-0 V-0 V-0

[0068] It can be seen from the above test results that the material of the present application has good mechanical properties and excellent flame retardant properties; combined with the comparative example, it can be seen that the addition of high temperature resistant filler in the present application can improve the temperature resistance, and the addition of flame retardant can improve the problem of reduced toughness caused by the introduction of high temperature resistant filler.

[0069] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An environmentally friendly flame retardant and high temperature resistant polycarbonate modified material, characterized in that: It includes the following raw materials in parts by weight: 80-100 parts of polycarbonate resin, 8-16 parts of flame retardant, 12-20 parts of high temperature resistant filler, 1-2 parts of coupling agent, and 2-3 parts of lubricant.

2. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1, characterized in that: The high temperature resistant filler is a mixture of one or more of quartz powder, silicon powder, mica powder and talcum powder in any proportion.

3. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1, characterized in that: The coupling agent is silane coupling agent KH560.

4. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1, characterized in that: The lubricant is pentaerythritol stearate.

5. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1, characterized in that: The flame retardant is prepared by the following steps: (1) Add p-phenylenediamine, sodium bicarbonate and ethanol to a dry three-necked flask, place the flask in an ice bath, stir and mix, and when the system temperature stabilizes at 0-2°C, slowly drop 1-chlorohexadecane under stirring. After the dropwise addition is complete, react at 0-2°C for 3 hours, and remove the solvent by rotary evaporation under reduced pressure to obtain intermediate 1; (2) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, add intermediate 1, sodium methoxide, methanol and 1,4-dioxane, and reflux for 6 hours. After the reaction is completed, perform rotary evaporation to remove methanol and 1,4-dioxane in the system to obtain intermediate 2; (3) In a three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, add intermediate 2 and 1,4-dioxane, stir for 20-30 minutes, introduce nitrogen for 8-10 minutes to replace the oxygen in the flask, and then add phosphorus oxychloride. Control the temperature during the addition not to exceed 30°C. Stir at a low speed first, then increase the stirring speed and raise the temperature. React for 6 hours. After the reaction is complete, filter and separate to obtain the product, wash with water, and dry to obtain a flame retardant.

6. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 5, characterized in that: In step (1), the ratio of p-phenylenediamine, sodium bicarbonate and 1-chlorohexadecane is 0.1 mol:8.4 g:0.1 mol.

7. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 5, characterized in that: In step (2), the ratio of the amount of intermediate 1 to sodium methoxide is 15 g:5.4 g.

8. The environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 5, characterized in that: In step (3), the ratio of the amount of intermediate 2 to phosphorus oxychloride is 17.2 g:5.1 g.

9. The method for preparing an environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1, characterized in that: The details are as follows: The polycarbonate resin, flame retardant and high temperature resistant filler are dried at 120°C for 5-6 hours, then the three, coupling agent and lubricant are mixed evenly according to a proportion, added into a twin-screw extruder, extruded, pulled, granulated and dried at 220°C-280°C to prepare the polycarbonate modified material.

10. Application of the environmentally friendly flame-retardant and high-temperature-resistant polycarbonate modified material according to claim 1 in the fields of telecommunications, IT and automobiles.

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