Polypropylene / waste circuit board non-metallic material composite material and preparation method thereof

Abstract

The present invention discloses a polypropylene / waste circuit board non-metallic material composite material, the raw materials of which include, by weight, 100 parts polypropylene and 40-50 parts modified waste circuit board non-metallic material. The modified waste circuit board non-metallic material comprises the following steps: mixing the waste circuit board non-metallic material, phosphorus oxychloride, and an organic solvent, conducting a primary reaction, and performing solid-liquid separation to obtain an intermediate A; mixing intermediate A, melamine, and water, conducting a secondary reaction, and performing solid-liquid separation to obtain an intermediate B; and melt-blending intermediate B with waste polypropylene to obtain the modified waste circuit board non-metallic material. The present invention also discloses a method for preparing the polypropylene / waste circuit board non-metallic material composite material. The present invention utilizes waste circuit board non-metallic material and waste polypropylene as raw materials, thereby saving costs, preventing environmental pollution from waste materials, and imparting excellent mechanical and flame retardant properties to the polypropylene.

Description

Technical Field

[0001] The present invention relates to the technical field of plastic recycling, and in particular to a polypropylene / waste circuit board non-metallic material composite material and a preparation method thereof. Background Art

[0002] Waste circuit boards primarily consist of substrates, electronic components, and printed circuit patterns. Substrates are typically composed of epoxy resin, glass fiber, ceramic fiber, and other materials; electronic components often contain valuable and precious metals; and printed circuit patterns are typically copper foil. While the technology for recycling the metal components of waste circuit boards is currently quite mature, non-metallic materials are often discarded as garbage, incinerated, or landfilled. This not only pollutes the environment but also results in a significant waste of resources. Research is needed on the recycling of non-metallic materials from waste circuit boards. Summary of the Invention

[0003] Based on the technical problems existing in the background technology, the present invention proposes a polypropylene / waste circuit board non-metallic material composite material and a preparation method thereof. The present invention selects waste circuit board non-metallic materials and waste polypropylene as raw materials, which saves costs, avoids waste pollution to the environment, and can make the polypropylene have good mechanical properties and flame retardant properties.

[0004] The present invention proposes a polypropylene / waste circuit board non-metallic material composite material, the raw materials of which include, by weight: 100 parts of polypropylene and 40-50 parts of modified waste circuit board non-metallic material;

[0005] Among them, in the preparation process of modified waste circuit board non-metallic materials, the waste circuit board non-metallic materials, phosphorus oxychloride, and organic solvent are mixed, a primary reaction is carried out, and solid-liquid separation is performed to obtain intermediate A; intermediate A, melamine, and water are mixed, a secondary reaction is carried out, and solid-liquid separation is performed to obtain intermediate B; intermediate B is melt-blended with waste polypropylene to obtain modified waste circuit board non-metallic materials.

[0006] Preferably, the non-metallic material of the waste circuit board contains epoxy resin, glass fiber and ceramic fiber, and the content of the epoxy resin is 60-80 wt%.

[0007] The above-mentioned polypropylene / waste circuit board non-metallic material composite material may contain: anti-ultraviolet agent, antioxidant, lubricant, etc., such as: ultraviolet absorber UV328, antioxidant 1010, lubricant polyethylene wax, etc.

[0008] The non-metallic materials of discarded circuit boards contain a large amount of epoxy resin, which contains a large number of active groups such as hydroxyl groups and epoxy groups. The present invention selects excessive phosphorus oxychloride to graft the hydroxyl groups in the non-metallic materials of the discarded circuit boards to obtain intermediate A, and then reacts excessive melamine with the epoxy groups in intermediate A and the hydroxyl groups in phosphorus oxychloride to obtain intermediate B. In this way, a large number of active amino groups are introduced into the non-metallic materials of the discarded circuit boards, and a large amount of N and P elements are introduced. These elements can interact with the glass fibers and ceramic fibers in the non-metallic materials of the discarded circuit boards to improve their flame retardant properties.

[0009] In addition, the inventors discovered that waste polypropylene will produce multiple carboxyl groups due to degradation. Melting and blending the waste polypropylene with intermediate B containing a large number of active amino groups will enable the waste polypropylene to be covalently bonded with the non-metallic materials of the waste circuit boards, and improve the compatibility of the non-metallic materials of the waste circuit boards in polypropylene; thus, it can be used as a filler to improve the mechanical properties of polypropylene.

[0010] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the waste circuit board non-metallic material to phosphorus oxychloride is 1:8-10.

[0011] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the temperature of the primary reaction is 70-80° C., and the reaction time is 8-12 hours.

[0012] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the intermediate A to melamine is 1:4-6.

[0013] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the temperature of the secondary reaction is 70-80° C., and the reaction time is 1-2 hours.

[0014] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the intermediate B to the waste polypropylene is 1:0.2-0.3.

[0015] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the melt blending temperature is 200-210° C. and the time is 30-60 min.

[0016] Preferably, in the preparation process of the modified waste circuit board non-metallic material, the organic solvent is dioxane.

[0017] The present invention also proposes a method for preparing the above-mentioned polypropylene / waste circuit board non-metallic material composite material, comprising the following steps: taking polypropylene and modified waste circuit board non-metallic material and mixing them evenly, granulating them through a twin-screw extruder, and injection molding to obtain the polypropylene / waste circuit board non-metallic material composite material.

[0018] Beneficial effects:

[0019] The non-metallic materials of discarded circuit boards contain a large amount of epoxy resin, which contains a large number of active groups such as hydroxyl groups and epoxy groups. The present invention selects excessive phosphorus oxychloride to graft the hydroxyl groups in the non-metallic materials of the discarded circuit boards to obtain intermediate A, and then reacts excessive melamine with the epoxy groups in intermediate A and the hydroxyl groups in phosphorus oxychloride to obtain intermediate B. In this way, a large number of active amino groups are introduced into the non-metallic materials of the discarded circuit boards, and a large amount of N and P elements are introduced. These elements can interact with the glass fibers and ceramic fibers in the non-metallic materials of the discarded circuit boards to improve their flame retardant properties.

[0020] In addition, the inventors discovered that waste polypropylene will produce multiple carboxyl groups due to degradation. Melting and blending the waste polypropylene with the intermediate B containing a large number of active amino groups will enable the waste polypropylene to be covalently bonded with the non-metallic materials of the waste circuit boards, and improve the compatibility of the non-metallic materials of the waste circuit boards in the polypropylene; thus, it can be used as a filler to improve the mechanical properties and flame retardancy of the polypropylene; and the glass fiber and ceramic fiber in the non-metallic materials of the waste circuit boards can further improve the mechanical properties of the polypropylene.

[0021] The present invention selects waste circuit board non-metallic materials and waste polypropylene as raw materials, uses them in polypropylene materials, saves costs, avoids environmental pollution caused by waste materials, and enables polypropylene to have good mechanical properties and flame retardant properties. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is described in detail below through specific embodiments.

[0023] Example 1

[0024] A polypropylene / waste circuit board non-metallic material composite material, the raw materials of which include, by weight: 10g polypropylene, 4g modified waste circuit board non-metallic material, 0.05g antioxidant, 0.1g anti-ultraviolet agent, and 0.3g lubricant;

[0025] Among them, in the preparation process of the modified waste circuit board non-metallic material, 5g of the waste circuit board non-metallic material (which contains epoxy resin, glass fiber and ceramic fiber, and the epoxy resin content is 80wt%) is taken, added to 300ml of dioxane and mixed, then 50g of phosphorus oxychloride is added and mixed, heated to 70°C, stirred and reacted for 12h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate A; 5g of intermediate A is mixed with 500ml of water, 30g of melamine is added and mixed, heated to 70°C, stirred and reacted for 2h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate B; 5g of intermediate B is mixed with 1.5g of waste polypropylene, heated to 200-210°C, melt blended for 60min, and extruded and granulated to obtain the modified waste circuit board non-metallic material.

[0026] The preparation method of the above-mentioned polypropylene / waste circuit board non-metallic material composite material includes the following steps: taking polypropylene, modified waste circuit board non-metallic material, antioxidant, anti-ultraviolet agent, and lubricant and mixing them evenly, extruding and granulating them through a twin-screw extruder, and injection molding to obtain the polypropylene / waste circuit board non-metallic material composite material.

[0027] Example 2

[0028] A polypropylene / waste circuit board non-metallic material composite material, the raw materials of which include, by weight: 10g polypropylene, 5g modified waste circuit board non-metallic material, 0.05g antioxidant, 0.1g anti-ultraviolet agent, and 0.3g lubricant;

[0029] Among them, in the preparation process of the modified waste circuit board non-metallic material, 5g of the waste circuit board non-metallic material (which contains epoxy resin, glass fiber and ceramic fiber, and the epoxy resin content is 60wt%) is taken, added to 300ml of dioxane and mixed, then 40g of phosphorus oxychloride is added and mixed, heated to 80°C, stirred and reacted for 8h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate A; 5g of intermediate A is mixed with 500ml of water, 20g of melamine is added and mixed, heated to 80°C, stirred and reacted for 1h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate B; 5g of intermediate B is mixed with 1g of waste polypropylene, heated to 200-210°C, melt blended for 30min, and extruded and granulated to obtain the modified waste circuit board non-metallic material.

[0030] The preparation method of the above-mentioned polypropylene / waste circuit board non-metallic material composite material includes the following steps: taking polypropylene, modified waste circuit board non-metallic material, antioxidant, anti-ultraviolet agent, and lubricant and mixing them evenly, extruding and granulating them through a twin-screw extruder, and injection molding to obtain the polypropylene / waste circuit board non-metallic material composite material.

[0031] Example 3

[0032] A polypropylene / waste circuit board non-metallic material composite material, the raw materials of which include, by weight: 10g polypropylene, 4.5g modified waste circuit board non-metallic material, 0.05g antioxidant, 0.1g anti-ultraviolet agent, and 0.3g lubricant;

[0033] Among them, in the preparation process of the modified waste circuit board non-metallic material, 5g of waste circuit board non-metallic material (which contains epoxy resin, glass fiber and ceramic fiber, and the epoxy resin content is 70wt%) is taken, added to 300ml of dioxane and mixed, then 45g of phosphorus oxychloride is added and mixed, heated to 75°C, stirred and reacted for 10h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate A; 5g of intermediate A is mixed with 500ml of water, 25g of melamine is added and mixed, heated to 75°C, stirred and reacted for 1.5h, cooled to room temperature, filtered to obtain the solid, washed, and vacuum dried at 60°C to obtain intermediate B; 5g of intermediate B is mixed with 1.3g of waste polypropylene, heated to 200-210°C, melt blended for 45min, and extruded and granulated to obtain the modified waste circuit board non-metallic material.

[0034] The preparation method of the above-mentioned polypropylene / waste circuit board non-metallic material composite material includes the following steps: taking polypropylene, modified waste circuit board non-metallic material, antioxidant, anti-ultraviolet agent, and lubricant and mixing them evenly, extruding and granulating them through a twin-screw extruder, and injection molding to obtain the polypropylene / waste circuit board non-metallic material composite material.

[0035] Comparative Example 1

[0036] Replace “modified waste circuit board non-metallic material” with “waste circuit board non-metallic material, which contains epoxy resin, glass fiber and ceramic fiber, and the content of epoxy resin is 70wt%”, and the rest is the same as Example 3.

[0037] Comparative Example 2

[0038] 5 g of waste circuit board non-metallic material (containing epoxy resin, glass fiber and ceramic fiber, and the epoxy resin content is 70 wt%) was mixed with 1.3 g of waste polypropylene, heated to 200-210° C. and melt-blended for 45 min, and extruded and granulated to obtain modified waste circuit board non-metallic material. Other aspects were the same as in Example 3.

[0039] Comparative Example 3

[0040] The modified waste circuit board non-metallic material was replaced by the intermediate B in Example 3, and the rest was the same as in Example 3.

[0041] Comparative Example 4

[0042] It does not contain non-metallic materials of modified waste circuit boards, and the rest is the same as Example 3.

[0043] The mechanical properties and flame retardant properties of the polypropylene / waste circuit board non-metallic material composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were tested, and the results are shown in Table 1.

[0044] The limiting oxygen index is tested according to ASTM D2863-97; the tensile strength and flexural strength are tested according to GB / T 1040-2018 and GB / T9341-2008.

[0045] Table 1 Test results

[0046]

[0047]

[0048] As can be seen from Table 1, the present invention has good flame retardancy and mechanical properties.

[0049] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A polypropylene / waste circuit board non-metallic material composite material, characterized in that: The raw materials include, by weight: 100 parts of polypropylene, 40-50 parts of modified waste circuit board non-metallic materials; In the preparation process of the modified waste circuit board non-metallic material, the waste circuit board non-metallic material containing hydroxyl and epoxy groups, phosphorus oxychloride, and an organic solvent are mixed and uniformly distributed, and a primary reaction is carried out to graft the phosphorus oxychloride with the hydroxyl groups in the waste circuit board non-metallic material, and solid-liquid separation is performed to obtain an intermediate A; the intermediate A, melamine, and water are mixed and uniformly distributed, and a secondary reaction is carried out to carry out solid-liquid separation to obtain an intermediate B containing amino groups; and the intermediate B is melt-blended with waste polypropylene to obtain the modified waste circuit board non-metallic material; Waste polypropylene contains carboxyl groups; The non-metallic materials of waste circuit boards contain epoxy resin, glass fiber and ceramic fiber, and the content of epoxy resin is 60-80wt%; In the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the waste circuit board non-metallic material to phosphorus oxychloride is 1:8-10; In the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the intermediate A to melamine is 1:4-6.

2. The polypropylene / waste circuit board non-metallic material composite material according to claim 1, characterized in that: In the preparation process of modified waste circuit board non-metallic materials, the temperature of a single reaction is 70-80° C., and the reaction time is 8-12 hours.

3. The polypropylene / waste circuit board non-metallic material composite material according to claim 1, characterized in that: In the preparation process of modified waste circuit board non-metallic materials, the temperature of the secondary reaction is 70-80° C. and the reaction time is 1-2 hours.

4. The polypropylene / waste circuit board non-metallic material composite material according to claim 1, characterized in that: In the preparation process of the modified waste circuit board non-metallic material, the weight ratio of the intermediate B to the waste polypropylene is 1:0.2-0.

3.

5. The polypropylene / waste circuit board non-metallic material composite material according to claim 1, characterized in that: In the preparation process of the modified waste circuit board non-metallic material, the melt blending temperature is 200-210° C. and the time is 30-60 minutes.

6. The polypropylene / waste circuit board non-metallic material composite material according to claim 1, characterized in that: In the preparation process of modified waste circuit board non-metallic materials, the organic solvent is dioxane.

7. A method for preparing the polypropylene / waste circuit board non-metallic material composite material according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: mixing polypropylene and modified waste circuit board non-metallic material, granulating through a twin-screw extruder, and injection molding to obtain a polypropylene / waste circuit board non-metallic material composite material.

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