CN116253948A - Filling master batch for plastics based on PCB material and preparation method - Google Patents

Abstract

A plastic filling master batch prepared based on PCB materials and a preparation method thereof, the composition and mass fraction of which are as follows: 100-300 parts of PCB powder, 79-100 parts of resin base material and 15-25 parts of auxiliary agent; the waste PCB is applied to plastic products, so that the energy is saved, the environment is protected, the recycling and the further utilization of the waste PCB are realized, and the ecological recycling and the ecological application can be realized; from the aspect of product application, energy sources can be saved, waste is effectively changed into valuables, and the method is applied to various plastic industries.

Description

Filling master batch for plastics based on PCB material and preparation method

Technical Field

The invention relates to the field of material recycling, in particular to a method for preparing filling master batch by using waste circuit boards.

Background

The functional plastic filling master batch mainly aims at strengthening the mechanical forms of plastic products, such as rigidity and toughness, and the like. The plastic filling master batch requires raw materials to have certain fineness, and has higher requirements on production process conditions. In the prior art, the raw materials used for various filling master batches currently known are all natural mines, and inorganic powder raw materials are processed through a series of production processes, for example: calcium carbonate, talc, barium sulfate, calcium thiophenoxide, wollastonite, and the like. However, due to the excessive centralized exploitation of the high-quality ore bodies, the high-quality ore bodies are rare at present, and the prices are continuously increased in recent years, so that the raw material cost is greatly increased.

After the improvement of the prior art, besides the inorganic mineral raw materials, the use of low molecular weight polymers as raw materials is also a commonly used mode at present. Usually these low molecular weight polymers are modified plastics or derivatives thereof, which, besides requiring the addition of costly auxiliaries, also have high temperature requirements for the preparation process and are difficult to achieve.

Currently, due to technological progress, electronic products are updated more and more rapidly, and electronic waste is more and more, and recycling such electronic waste becomes an important problem in the current fields of environmental protection and resource recycling, wherein recycling of waste Printed Circuit Boards (PCBs) is one of the main problems of electronic waste disposal.

Printed Circuit Boards (PCBs) are fundamental components of electronic information products and are of a wide variety. Most household electrical appliances such as televisions and washing machines are single-sided copper-clad plates (FR-14) formed by hardening paper fibers with phenolic resin. At present, china enters the scrapping peak period of electronic home appliances, and the scrapped PCBs in the scrapped home appliances account for about 3%, so that the presumption is that the scrapped amount of the paper-based PCBs is huge. The metal in the waste PCB accounts for about 30%, which is always the key point of recycling; but about 70% of the non-metals are either discarded or incinerated, as opposed to metal recovery processes. In the local area in the south, a large amount of organic pollutants generated in the process of illegally incinerating the waste PCB and recycling metals are diffused into an environment medium, so that serious environmental pollution is caused.

The current treatment and recycling method of waste PCBs is focused on recycling copper and precious metals, whereas for non-metallic components (main components are short glass fibers, thermosetting resins, etc.) with a weight ratio of up to 60-80% in waste PCBs, no reasonable and effective recycling method has been available so far.

The thermosetting resins used in PCB production cannot be re-pelletized like thermoplastic materials, and how to effectively use them is a difficulty in recycling waste PCBs. At present, the application of waste PCB waste metal powder is mainly focused on the use of FR-4 containing a large amount of glass fiber as filler for manufacturing building materials, thermoplastic or thermosetting rubber and the like.

As the waste polypropylene and the waste printed circuit board nonmetal powder (waste PCB powder) are waste materials, if a composite material with excellent performance can be prepared from the waste polypropylene and the waste PCB nonmetal powder, the waste PCB can be recycled and further utilized, and the waste PCB has no doubt important economic and social significance.

In view of the foregoing, there is a great need for reduced cost and better performing filler concentrates in plastic processing, and how to dispose of the recovery and reuse of circuit boards.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a filling master batch applied to plastics and a preparation method thereof, wherein the recovered PCB is processed into powder and applied to the production of the plastic filling master batch.

The plastic filling master batch prepared based on the PCB material is characterized by comprising the following components in percentage by mass: 100-300 parts of PCB powder, 79-100 parts of resin base material and 15-25 parts of auxiliary agent.

The PCB powder is a non-metallic powder from a waste printed circuit board.

The resin substrate is selected from: PE, PP, PS, PA, ABS, EVA, one of the following;

the auxiliary agent comprises the following components: modifiers, dispersants, and lubricants.

The auxiliary agent also comprises: a coupling agent. The coupling agent is used for preparing the modified PCB powder.

The auxiliary agent comprises the following components in parts by weight: 3-7 parts of talcum powder, 2-6 parts of stearic acid and 4-7 parts of polyethylene wax (PE wax). The coupling agent is 7% -12% of the PCB powder; preferably 10%.

The coupling agent is gamma-aminopropyl triethoxysilane.

The particle size of the PCB powder is 100-300 mu m; preferably 200 μm.

A method of preparing a plastic filling masterbatch, the method comprising the steps of:

(1) Removing surface components from the waste printed circuit board, and carrying out crushing treatment, sorting treatment, collecting and sieving treatment to obtain nonmetal powder of the printed circuit board;

(2) Adding the crushed non-metal powder of the waste printed circuit board into a coupling agent for surface treatment;

(3) Respectively weighing a resin base material, a dispersing agent, a modifying agent and a lubricating agent, and then pouring the materials into a high-speed mixer for stirring to prepare a premix;

(4) And (3) placing the premix and the non-metal particles of the waste printed circuit board subjected to surface treatment into a homodromous double-screw granulator for granulating, hot cutting and cooling to obtain the plastic filling master batch.

Compared with the prior art, the invention has the beneficial effects that: energy saving and environmental protection, realizes the recycling and further utilization of waste PCB, and can realize ecological recycling and ecological application.

The invention is applied to plastic products by utilizing waste PCBs. From the aspect of product application, energy sources can be saved, waste is effectively changed into valuables, and the method is applied to various plastic industries.

The invention has been successfully applied to filling masterbatches and plastic products, and experimental data are higher than the performance index of the substituted calcium carbonate.

The filling master batch has wide application field. The production cost is reduced, the compatibility between the raw materials of the product is improved, and the quality of the product is ensured.

Drawings

FIG. 1 is a flow chart of a preparation process.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The invention discloses a filling master batch for plastics, which is used for avoiding adding the traditional filling master batch when processing plastics and reducing the manufacturing cost of the plastics.

The processes used in the following examples 1 to 3 are substantially identical, and the following table is referred to for different specific compounding parameters (if not specified, the raw materials in the following examples are all commercially available):

plastics with different filling concentrates were tested,

detecting a sample: is provided by Tianjin Longbao energy saving technology Co.

The detection items and related information are shown in the following table.

The polypropylene is F401 type, available from Yanshan petrochemical company.

Example 1

A filling master batch for plastics comprises the following components in parts by weight: 100 Parts of Polypropylene (PP), 260 parts of PCB powder, 6 parts of talcum powder, 4 parts of stearic acid, 6 parts of polyethylene wax (PE wax) and 3 parts of silane coupling agent.

Wherein the average particle diameter of the PCB powder is 200 mu m.

1) Preparation of filling masterbatch containing PCB powder

The formula comprises the following components: 100 Parts of Polypropylene (PP), 260 parts of PCB powder, 6 parts of talcum powder, 4 parts of stearic acid, 6 parts of polyethylene wax (PE wax) and 3 parts of silane coupling agent.

And adding the components into a double-screw extruder through a screw feeding machine for extrusion to obtain the filling master batch containing the PCB powder.

2) Preparation of plastics comprising a filling masterbatch comprising PCB powder

60 parts by weight of polypropylene and 40 parts by weight of the filling master batch of the PCB powder prepared in example 1 were prepared into plastics by an injection molding method.

Comparative example 1:

1) Preparation of a filling masterbatch containing calcium carbonate

The formula comprises the following components: 100 Parts of Polypropylene (PP), 260 parts of calcium carbonate, 6 parts of talcum powder, 4 parts of stearic acid, 6 parts of polyethylene wax (PE wax) and 3 parts of silane coupling agent.

The components are added into a double-screw extruder through a screw feeding machine to be extruded, so as to obtain the filling master batch containing calcium carbonate.

2) Preparation of plastics comprising a filling masterbatch containing calcium carbonate

60 parts by weight of polypropylene and 40 parts by weight of the calcium carbonate-containing filler masterbatch prepared in comparative example 1 were prepared into plastics by an injection molding method.

Example 1 test comparative results are shown in the following table.

Examples 2 and 3

The preparation method of each example is the same as that of example 1, except that the components and the amounts thereof are as shown in the following table.

The test results show that the indexes such as melt fluidity, density, fiber content/ash content, bending strength, tensile strength, elongation at break, cantilever impact strength and the like of the filling master batch containing the PCB powder are obviously superior to those of the filling master batch containing calcium carbonate, so that the plastic toughness of the filling master batch containing the PCB powder is enhanced, the plastic deformation stress is stronger, the extensibility is stronger, the impact strength is improved, the processing is easier, the number of finished products can be obviously increased, and the cost is saved.

The invention also relates to a preparation method of the filling master batch for plastics, which comprises the following steps:

the preparation method of the filling master batch for the plastic comprises the following steps:

A. treatment process of nonmetallic material of printed circuit board

Removing surface components from the waste printed circuit board, and carrying out crushing treatment, sorting treatment, collecting and sieving treatment to obtain nonmetal powder of the printed circuit board; the particle size of the nonmetal powder of the printed circuit board is 100 meshes;

in the crushing treatment, the adopted equipment is an ultrafine pulverizer (RT-25, taiwan) for crushing and sieving;

the sorting treatment is electrostatic sorting, and the adopted equipment is a YD3040211I type high-voltage electric selector (the external dimension is 900mm multiplied by 872mm multiplied by 2000mm, the roller diameter is 30cm, the treatment capacity is 0.05-0.20 t/h, and the transmission power is 0.6 kW);

the separation treatment can also be carried out by adopting various methods to optimize the treatment effect, and the adopted equipment is an eddy current separator YW type eddy current metal (non-iron) recycling machine which is produced by a Changsha mining and metallurgy institute;

a-b. Pouring crushed nonmetal particles of the waste printed circuit board into a high-speed mixer, stirring at high speed for dehumidification, and adding a coupling agent (if used) when the temperature of the material rises to 100 ℃ for surface treatment. And cooling the treated powder and packaging for later use.

Wherein, the silane coupling agent and industrial alcohol are mixed for 20 to 30 minutes at room temperature according to the volume ratio of 1 to 5:5 to 10, and the silane coupling agent after alcoholysis is obtained; the silane coupling agent is gamma-aminopropyl triethoxysilane, which is purchased from Nanjing dawn photonics factory;

mixing the alcoholysis silane coupling agent with the non-metal powder of the printed circuit board, and stirring to obtain mixed powder; the weight ratio of the silane coupling agent after alcoholysis to the nonmetal powder of the printed circuit board is 1-5:95-99, the stirring treatment is carried out for 10-30 min at the rotating speed of 1300-2000 rpm/min, and the adopted equipment is a high-speed stirrer;

B. the resin base material, the dispersant, the modifier and the lubricant are weighed respectively and then poured into a high-speed mixer for stirring.

B-a, pouring 100kg of polypropylene into a high-speed mixer with the rotating speed of 900 revolutions per minute for stirring for standby.

B-B, pouring 6kg of talcum powder, 4kg of stearic acid and 6kg of polyethylene wax (PE wax) into a high-speed mixer with the rotation speed of 900 revolutions per minute for mixing at one time until friction heat generated by mixing raises the temperature of the materials to 80 ℃ for discharging, and then sending the mixed materials into a cooling stirrer for stirring and cooling to the ambient temperature (0-40 ℃).

B-c, drying the mixed powder; in the drying treatment, the time is 1.5-3 h, the temperature is 60-100 ℃, and the adopted equipment is a DZF-200 type vacuum drying oven;

C. respectively placing the non-metal particles of the waste printed circuit board subjected to surface treatment and the polypropylene particles subjected to pre-mixing treatment into a storage vat, adding the storage vat into a parallel double-screw extruder according to a certain proportion, carrying out melt extrusion granulation, extruding a die bracing, cooling by a cooling water tank, granulating, sieving by a vibrating screen, carrying out forced air drying, weighing and packaging.

C-a, mixing the non-metal material of the silanized printed circuit board and the polypropylene (PP) subjected to the mixing treatment in an extruder according to the proportion of each component, and granulating to obtain granules; in the granulation treatment, the temperatures of all areas of the double-screw extruder are as follows in sequence: the first heating zone temperature t1=100 to 120 ℃, the second heating zone temperature t2=130 to 140 ℃, the third heating zone temperature t3=150 to 160 ℃, the first fourth heating zone temperature t4=160 to 170 ℃, the fifth heating zone temperature t5=170 to 180 ℃, the sixth heating zone temperature t6=180 to 190 ℃, the seventh heating zone temperature t7=190 to 200 ℃, the eighth heating zone temperature t8=190 to 200 ℃, the ninth heating zone temperature t9=190 to 200 ℃, and the extrusion die temperature T die=180 to 205 ℃. The rotating speed of the screw is 140-200 rpm/min; the equipment used was a ZSK-25WLE twin screw extruder, purchased from WP, germany; the polypropylene is F401 type and is purchased from the Yanshan petrochemical company;

c-b, drying the obtained granules to obtain dried granules; in the drying treatment, the time is 24-48 h, the temperature is 60-100 ℃, and the adopted equipment is a DZF-200 type vacuum drying oven.

Finally, it should be noted that: the foregoing is merely illustrative of the present invention and is not to be construed as limiting thereof, and although the present invention has been described in detail, it will be apparent to those skilled in the art that modifications may be made to the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The plastic filling master batch prepared based on the PCB material is characterized by comprising the following components in percentage by mass: 100-300 parts of PCB powder, 79-100 parts of resin base material and 15-25 parts of auxiliary agent.

2. The plastic filling masterbatch of claim 1, wherein the PCB powder is a non-metallic powder from a waste printed circuit board.

3. The plastic filling masterbatch of claim 1, wherein the resin substrate is selected from the group consisting of: PE, PP, PS, PA, ABS, EVA, one of the following; the auxiliary agent comprises the following components: modifiers, dispersants, and lubricants.

4. The plastic filling masterbatch of claim 3, wherein the adjuvant further comprises: a coupling agent.

5. The plastic filling master batch of claim 4, wherein the coupling agent is used to prepare modified PCB powder.

6. A plastic filling masterbatch according to claim 3, characterized in that the auxiliary comprises the components in parts by weight: 3-7 parts of talcum powder, 2-6 parts of stearic acid and 4-7 parts of polyethylene wax (PE wax).

7. The plastic filling masterbatch according to claim 6, characterized in that the auxiliary comprises the components in parts by weight: the coupling agent is 7% -12% of the PCB powder; preferably 10%.

8. The plastic filling master batch according to claim 4, wherein the auxiliary agent is gamma-aminopropyl triethoxysilane.

9. The plastic filling masterbatch of claim 1, wherein; the particle size of the PCB powder is 100-300 mu m; preferably 200 μm.

10. A process for preparing a plastic filling masterbatch as claimed in claims 1-9, said process comprising the steps of:

(1) Removing surface components from the waste printed circuit board, and carrying out crushing treatment, sorting treatment, collecting and sieving treatment to obtain nonmetal powder of the printed circuit board;

(2) Adding the crushed non-metal powder of the waste printed circuit board into a coupling agent for surface treatment;

(3) Respectively weighing a resin base material, a dispersing agent, a modifying agent and a lubricating agent, and then pouring the materials into a high-speed mixer for stirring to prepare a premix;

(4) And (3) placing the premix and the non-metal particles of the waste printed circuit board subjected to surface treatment into a homodromous double-screw granulator for granulating, hot cutting and cooling to obtain the plastic filling master batch.

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