阅读说明：本技术 一种塑料用煤矸石功能填充母粒及其制备方法 (Coal gangue function filling master batch for plastics and preparation method thereof ) 是由 李成 王鹏 熊松阳 陈楠楠 周海 于 2021-08-30 设计创作，主要内容包括：本发明属于高分子技术领域,具体涉及一种塑料用煤矸石功能填充母粒及其制备方法。本发明填充母粒按重量份计,包括以下组分：载体树脂20-40份、煤矸石50-80份、偶联剂0.5-2份、分散剂0.3-0.8份、相容剂4-6份；所述煤矸石包括煅烧煤矸石和表面改性煤矸石；所述煅烧煤矸石占煤矸石总量的30-50％；所表面改性煤矸石占煤矸石总量的50-70％。本发明的煤矸石功能填充母粒以改性的煤矸石为填充料,用于制备薄膜、管材、片材、注塑等塑料制品,能提高塑料产品的绝缘性能、阻燃性能和力学性能；该制备方法通过分批密炼,将废弃物煤矸石进行资源化利用,可减少环境的污染,降低塑料生产成本。(The invention belongs to the technical field of polymers, and particularly relates to a coal gangue functional filling master batch for plastics and a preparation method thereof. The filling master batch comprises the following components in parts by weight: 20-40 parts of carrier resin, 50-80 parts of coal gangue, 0.5-2 parts of coupling agent, 0.3-0.8 part of dispersing agent and 4-6 parts of compatilizer; the coal gangue comprises calcined coal gangue and surface modified coal gangue; the calcined coal gangue accounts for 30-50% of the total amount of the coal gangue; the surface modified coal gangue accounts for 50-70% of the total amount of the coal gangue. The coal gangue functional filling master batch takes the modified coal gangue as a filler, is used for preparing plastic products such as films, pipes, sheets, injection molding and the like, and can improve the insulating property, the flame retardant property and the mechanical property of the plastic products; the preparation method carries out resource utilization on the waste coal gangue by banburying in batches, so that the environmental pollution can be reduced, and the production cost of plastics can be reduced.)

1. The coal gangue functional filling master batch for plastics is characterized by comprising the following components in parts by weight: 15-40 parts of carrier resin, 50-80 parts of coal gangue, 0.5-2 parts of coupling agent, 0.3-0.8 part of dispersing agent and 4-6 parts of compatilizer;

the coal gangue comprises calcined coal gangue and surface modified coal gangue;

the calcined coal gangue accounts for 30-50% of the total amount of the coal gangue; the surface modified coal gangue accounts for 50-70% of the total amount of the coal gangue.

2. The functional filling master batch of the coal gangue for plastics as claimed in claim 1, wherein the calcining temperature of the calcined coal gangue is 550-.

3. The gangue functional filling masterbatch for plastics of claim 1, wherein the modification method of the surface-modified gangue comprises: crushing the coal gangue to 180 meshes by 150-fold sand, adding the crushed coal gangue into a stirrer, adding acid, stirring the mixture for 20 to 30 minutes at the rotating speed of 1000r/min by 500-fold sand, washing the mixture for 2 to 3 times by using water, and drying the mixture at 105 ℃; and then adding the dried coal gangue into the stirrer again, adding a modifier with the coal gangue content of 1-3%, and stirring at the rotating speed of 1500-2000r/min for 20-40min to obtain the surface modified coal gangue.

4. The gangue functional filler masterbatch for plastics of claim 3, wherein the acid is hydrochloric acid or phosphoric acid, and the mass ratio of the acid to the gangue is 0.5-0.7: 1.

5. the coal gangue functional filling master batch for plastics according to claim 3, wherein the modifier is any one of aluminate and bis (dioctyl phosphate) oxyacetate titanate.

6. The gangue functional filler masterbatch for plastics of claim 1, wherein the carrier resin is at least one of polyethylene, polypropylene, polystyrene, ABS, polyethylene terephthalate, polylactic acid, and polybutylene succinate.

7. The coal gangue functional filling master batch for plastics as claimed in claim 1, wherein the coupling agent is any one of KH550, KH560 and KH 792.

8. The coal gangue functional filling master batch for plastics according to claim 1, wherein the dispersing agent is any one of polyethylene wax or zinc stearate.

9. The coal gangue functional filling masterbatch for plastics of claim 1, wherein the compatibilizer is maleic anhydride grafted polyolefin.

10. The preparation method of the coal gangue functional filling masterbatch for plastics of any one of claims 1 to 9, which is characterized by comprising the following steps:

s1, weighing raw materials according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing for 20-30 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, mixing, carrying out secondary banburying, and carrying out banburying for 30-40min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at the temperature of 130-150 ℃ to obtain the coal gangue functional filling master batch.

Technical Field

The invention belongs to the technical field of polymers, and particularly relates to a coal gangue functional filling master batch for plastics and a preparation method thereof.

Background

The plastic filling master batch is used as an additive in the plastic processing process, and is a high filling master batch which is obtained by mainly using inorganic powder, carrier resin and a modification auxiliary agent through extrusion granulation molding and can meet the molding process requirements of plastic products. The plastic filling master batch has the first purpose of increasing the corresponding performance of the plastic and the second purpose of reducing the production cost of the plastic.

The coal gangue is solid waste discharged in the coal mining process and the coal washing process, is a black grey rock which has lower carbon content and is harder than coal and is associated with a coal bed in the coal forming process, comprises tunneling gangue in the tunneling process, gangue extracted from a top plate, a bottom plate and an interlayer in the mining process and washing gangue extracted in the coal washing process, has large quantity and low price, and mainly comprises Al₂O₃、SiO₂. The ash melting point (the temperature which is measured under the specified conditions and causes deformation, softening and flowing of the coal gangue) of the coal gangue is quite high, the lowest temperature is 1050 ℃, and the highest temperature can reach about 1800 ℃, so the coal gangue can be used as a refractory material; meanwhile, the coal gangue also has certain expansibility, plasticity and contractibility, and certain hardness and strength. By combining the characteristics of the coal gangue, the coal gangue is a good choice when being applied to plastic processing, and meanwhile, the problem of environmental pollution caused by the coal gangue can be reduced.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the coal gangue functional filling master batch for plastics and the preparation method thereof. The filling master batch takes the modified coal gangue as a filler, is used for preparing plastic products such as films, pipes, sheets, injection molding and the like, can improve the insulating property, the flame retardant property and the mechanical property of the plastic products, and simultaneously utilizes the coal gangue as resources, so that the environmental pollution can be reduced, and the production cost of the plastic is reduced.

In order to achieve the purpose, the invention provides a coal gangue functional filling master batch for plastics, which comprises the following components in parts by weight: 15-40 parts of carrier resin, 50-80 parts of coal gangue, 0.5-2 parts of coupling agent, 0.3-0.8 part of dispersing agent and 4-6 parts of compatilizer;

the coal gangue comprises calcined coal gangue and surface modified coal gangue;

the calcined coal gangue accounts for 30-50% of the total amount of the coal gangue; the surface modified coal gangue accounts for 50-70% of the total amount of the coal gangue.

The calcined coal gangue in the technical scheme has better insulation resistance, large specific surface area and high adsorption activity; the coal gangue subjected to surface modification has the advantages of small particle size, increased surface activity, high resistivity and improved mechanical property, can be fully mixed with carrier resin as a filler, and can obviously improve the insulating property and the mechanical property when being used for plastic products.

Further, in the technical scheme, the calcining temperature of the calcined coal gangue is 550-800 ℃, the calcining time is 30-40min, and the crushing particle size is 200-250 meshes. In the technical scheme, the coal gangue can generate some active minerals such as calcium silicate (CaO. Si 0) through the transient calcination at the temperature of 800 ℃ under the temperature of 550-₂) And dicalcium silicate (2 CaO. Si 0)₂) Etc., having higher activity; meanwhile, carbon in the coal gangue can be removed through calcination, the color becomes light, and the application range and the flame retardant property of the coal gangue can be improved.

Further, the modification method of the surface modified coal gangue in the technical scheme comprises the following steps: crushing the coal gangue to 180 meshes by 150-fold sand, adding the crushed coal gangue into a stirrer, adding acid, stirring the mixture for 20 to 30 minutes at the rotating speed of 1000r/min by 500-fold sand, washing the mixture for 2 to 3 times by using water, and drying the mixture at 105 ℃; and then adding the dried coal gangue into the stirrer again, adding a modifier with the coal gangue content of 1-3%, and stirring at the rotating speed of 1500-2000r/min for 20-40min to obtain the surface modified coal gangue. In the technical scheme, the coal gangue is crushed and then soaked in acid, so that part of iron in the coal gangue can be removed, the color is lightened, the application range of the coal gangue can be improved, and the mechanical property of the coal gangue is further improved by performing surface treatment on the coal gangue through a modifier after washing.

Further, in the above technical scheme, the acid is hydrochloric acid or phosphoric acid, and the mass ratio of the acid to the coal gangue is 0.5-0.7: 1. in the technical scheme, the strong acid is used for removing iron in the coal gangue, so that the color and the insulating property of the coal gangue can be improved.

Further, in the above technical scheme, the modifier is any one of aluminate and bis (dioctyl phosphate) oxyacetate titanate. In the technical scheme, the aluminate is a coupling agent, can activate and modify inorganic powder, not only has the effect of stabilizing quality, but also can reduce the color and toxicity of the inorganic powder and improve the thermal stability of the inorganic powder, and is convenient to use and low in cost; the bis (dioctyl phosphate) oxygen-containing acetic acid titanate is also a coupling agent, contains alkoxy and can be chemically combined with hydroxyl on the surface of the coal gangue, so that the elasticity and tensile strength of the coal gangue can be improved, and the mechanical property of the coal gangue can be improved.

Further, in the above technical scheme, the carrier resin is at least one of polyethylene, polypropylene, polystyrene, ABS, polyethylene terephthalate, polylactic acid, and polybutylene succinate.

Further, in the above technical scheme, the coupling agent is any one of KH550, KH560 and KH 792. KH550 is amino functional group silane, and can improve bending strength and shearing strength when applied to mineral fillers, and improve dispersibility of the fillers in polymers; KH560 is an epoxy-containing coupling agent used for inorganic filler to improve its strength and dispersibility; KH792 acts as a coupling agent to couple the organic polymer and inorganic material into a single chemical bond to improve the various physical and mechanical properties of the polymer.

Further, the dispersant in the above technical scheme is any one of polyethylene wax or zinc stearate. In the technical scheme, a long chain molecule of the polyethylene wax is provided with a certain amount of ester groups or soap groups, so that the internal and external lubricating effects on PVC, PE, PP and ABS are balanced, the dispersing effect is good, and the transparency is good; zinc stearate is a metal soap, suitable for dispersing polyolefins, ABS, etc.

Further, in the above technical scheme, the compatibilizer is maleic anhydride grafted polyolefin. Specifically, the maleic anhydride-grafted polyolefin may be maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-grafted POE, or the like.

The invention also provides a preparation method of the coal gangue function filling master batch for plastics, which comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing for 20-30 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, mixing, carrying out secondary banburying, and carrying out banburying for 30-40min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at the temperature of 130-150 ℃ to obtain the coal gangue functional filling master batch.

According to the technical scheme, the calcined coal gangue is mixed with the carrier resin and is subjected to banburying under the action of the dispersing agent, the calcined coal gangue and the carrier resin are fully mixed and reacted, the flame retardant property and the mechanical property of the resin are improved, then the surface modified coal gangue, the coupling agent and the compatilizer are added to carry out secondary banburying reaction, the resin and the coal gangue are coupled and compatible into a whole, the obtained master batch has the characteristics of the resin and the coal gangue, and the comprehensive performance is improved.

The invention has the beneficial effects that:

1. the coal gangue used in the invention is divided into calcined coal gangue and surface modified coal gangue, the adsorption activity and fire resistance of the coal gangue can be improved by calcination, and the surface activity, insulativity and mechanical property of the coal gangue can be improved by surface modified coal gangue.

2. The gangue functional filling master batch obtained by mixing twice and banburying twice to modify the carrier resin has partial properties of gangue, and the insulation property, the flame retardant property and the mechanical property of the gangue functional filling master batch are improved.

3. When the coal gangue functional filling master batch is used for preparing plastic products such as films, pipes, sheets, injection molding and the like, and the addition amount is 10-15%, the effect is obviously improved.

4. The preparation method has simple process, can utilize the waste coal gangue as resources, can reduce the environmental pollution and can also reduce the production cost of plastics.

Detailed Description

The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials in the following examples are all commercially available products and are commercially available, unless otherwise specified.

The present invention is described in further detail below with reference to examples:

example 1

The calcining method for calcining the coal gangue comprises the following steps: calcining coal gangue at 550 deg.C for 40min, cooling, and pulverizing to 250 mesh.

The modification method of the surface modified coal gangue comprises the following steps: pulverizing coal gangue to 150 mesh, adding into a stirrer, adding acid, stirring at 1000r/min for 20min, washing with water for 2 times, and drying at 105 deg.C; and then adding the dried coal gangue into the stirrer again, adding a modifier accounting for 1% of the coal gangue, and stirring at the rotating speed of 1500r/min for 40min to obtain the surface modified coal gangue.

Example 2

The calcining method for calcining the coal gangue comprises the following steps: calcining coal gangue at 600 deg.C for 35min, cooling, and pulverizing to 220 mesh.

The modification method of the surface modified coal gangue comprises the following steps: pulverizing coal gangue to 160 mesh, adding into a stirrer, adding acid, stirring at 800r/min for 25min, washing with water for 3 times, and drying at 105 deg.C; and then adding the dried coal gangue into the stirrer again, adding a modifier accounting for 2% of the coal gangue, and stirring at the rotating speed of 1800r/min for 30min to obtain the surface modified coal gangue.

Example 3

The calcining method for calcining the coal gangue comprises the following steps: calcining coal gangue at 800 deg.C for 30min, cooling, and pulverizing to 200 mesh.

The modification method of the surface modified coal gangue comprises the following steps: pulverizing coal gangue to 180 mesh, adding into a stirrer, adding acid, stirring at 500r/min for 30min, washing with water for 3 times, and drying at 105 deg.C; and then adding the dried coal gangue into the stirrer again, adding a modifier with the coal gangue content of 3%, and stirring at the rotating speed of 2000r/min for 20min to obtain the surface modified coal gangue.

Example 4

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 15.4% of polyethylene, 24% of calcined coal gangue, 56% of surface modified coal gangue, 0.5% of KH550, 0.3% of polyethylene wax and 3.8% of maleic anhydride grafted polyethylene; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of example 1.

The preparation method comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing for 20 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, mixing, carrying out secondary banburying, and carrying out banburying for 340min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at 130 ℃ to obtain the coal gangue functional filling master batch.

Example 5

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 24.0% of polypropylene, 28% of calcined coal gangue, 42% of surface modified coal gangue, 1% of KH560, 0.8% of zinc stearate and 4.2% of maleic anhydride grafted polypropylene; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of the embodiment 2.

The preparation method comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing, wherein the internal mixing time is 25 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, mixing, carrying out secondary banburying, and carrying out banburying for 35min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at 140 ℃ to obtain the coal gangue functional filling master batch.

Example 6

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 32.5% of polystyrene, 30% of calcined coal gangue, 30% of surface modified coal gangue, 2% of KH792, 0.5% of zinc stearate and 5% of maleic anhydride grafted POE; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of example 3.

The preparation method comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing for 30 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, mixing, carrying out secondary banburying, and carrying out banburying for 30min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at 150 ℃ to obtain the coal gangue functional filling master batch.

Comparative example 1

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 24.0% of polypropylene, 70% of coal gangue, 1% of KH560, 0.8% of zinc stearate and 4.2% of maleic anhydride grafted polypropylene. The preparation process is as in example 5.

Comparative example 2

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 24.0% of polypropylene, 7% of calcined coal gangue, 63% of surface modified coal gangue, 1% of KH560, 0.8% of zinc stearate and 4.2% of maleic anhydride grafted polypropylene; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of the embodiment 2. The preparation process is as in example 5.

Comparative example 3

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 24.0% of polypropylene, 49% of calcined coal gangue, 21% of surface modified coal gangue, 1% of KH560, 0.8% of zinc stearate and 4.2% of maleic anhydride grafted polypropylene; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of the embodiment 2. The preparation process is as in example 5.

Comparative example 4

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 24.0% of polypropylene, 28% of calcined coal gangue, 42% of surface modified coal gangue, 1% of KH560, 0.8% of zinc stearate and 4.2% of maleic anhydride grafted polypropylene; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of the embodiment 2.

The preparation method comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin, the calcined coal gangue, the surface modified coal gangue, the zinc stearate and the maleic anhydride grafted polypropylene, adding the mixture into an internal mixer, and internally mixing for 25min to obtain an internally mixed product;

and S3, inputting the banburying product in the S2 into a double-screw extruder, and extruding and granulating at 140 ℃ to obtain the coal gangue functional filling master batch.

Example 6

The gangue functional filling master batch for plastics comprises the following components in parts by weight: 32.5% of polystyrene, 30% of calcined coal gangue, 30% of surface modified coal gangue, 2% of KH792, 0.5% of zinc stearate and 5% of maleic anhydride grafted POE; wherein the calcined coal gangue and the surface modified coal gangue are prepared by the method of example 3.

The preparation method comprises the following steps:

s1, weighing raw material components according to a ratio;

s2, uniformly mixing the carrier resin and the calcined coal gangue to obtain a mixture;

s3, adding the mixture obtained in the step S2 and a dispersing agent into an internal mixer for primary internal mixing for 30 min;

s4, adding the surface modified coal gangue, the coupling agent and the compatilizer after primary banburying in S3, carrying out secondary banburying, and carrying out banburying for 30min to obtain a banburying product;

s5, inputting the banburying product in the S4 into a double-screw extruder, and extruding and granulating at 150 ℃ to obtain the coal gangue functional filling master batch.

The master batches prepared in examples 4 to 6 and comparative examples 1 to 4 were subjected to performance tests according to the QBT1126-1991 polyolefin filler masterbatch standard, and the results are shown in Table 1.

TABLE 1 Master batch Performance parameters

Item	Example 4	Example 5	Example 6	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
								Whiteness degree%	57	62	68	38	58	56	60
Density, g/cm2	1.79	1.67	1.58	2.03	1.76	1.49	1.63
								Melt flow Rate, g/10min	1.8	0.83	5.8	0.96	0.90	0.89	0.85

As can be seen from the results in table 1, the masterbatch obtained by using the calcined and modified coal gangue as the filler has higher whiteness and lower density than the masterbatch obtained by using the conventional coal gangue; the whiteness and density of the master batch prepared by the invention through twice banburying are slightly superior to those of the master batch obtained through once banburying; the formula and the preparation method of the invention have better effect.

After the master batches prepared in examples 4-6 and comparative examples 1-4 are mixed with polypropylene, plastic sample bars are prepared, and various performance tests are carried out according to the standard in GB/T1040-2018, and the results are shown in Table 2. In test example 1, 10% of the master batch prepared in example 4 was added; test example 2 added 30% of the master batch prepared in example 5, and test example 3 added 50% of the master batch prepared in example 6; test example 4 30% of the master batch prepared in comparative example 1 was added; test example 5 30% of the master batch prepared in comparative example 2 was added; test example 6 30% of the master batch prepared in comparative example 3 was added; test example 7 30% of the master batch prepared in comparative example 4 was added.

TABLE 2 Property parameters of the blends of masterbatch and Polypropylene

The results in Table 2 show that the performance indexes of the test examples 1-3 are superior to those of the test examples 4-7, which shows that the filling master batch prepared by the preparation method of the invention can effectively improve the mechanical property, the insulating property and the flame retardant property of the polypropylene product.

From the test results of the test examples 2 and 4, it can be seen that when the conventional coal gangue filled masterbatch is used, the chemical properties, the insulating properties and the flame retardant properties of the polypropylene product are slightly improved, but the improvement effect is obviously inferior to that of the masterbatch obtained by the method of the present invention when the masterbatch is used for the polypropylene product. As can be seen from the test results of Experimental example 2 and Experimental examples 5-6, when the ratio of the calcined coal gangue to the surface-modified coal gangue is less than 30%: 70% or more than 70%: at 30%, the performance improvement of the polypropylene product is not as good as that of the polypropylene product using the master batch obtained by the proportion of the invention, and particularly, the improvement of the mechanical property is greatly poor. From the test results of test example 2 and test example 7, it can be seen that the performance of the master batch obtained by mixing twice and banburying twice by using the method of the present invention is improved better than the master batch obtained by mixing once and banburying once, which indicates that the preparation method of the present invention has better effect.

In conclusion, the master batch prepared by the method meets the requirement of the standard of the filling master batch, the insulation performance, the flame retardant performance and the mechanical property of a plastic product can be obviously improved by adding the master batch into the plastic product according to the amount of 10-50%, and meanwhile, the method can utilize the coal gangue as resources, reduce the environmental pollution and reduce the production cost of the plastic.

Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.