阅读说明：本技术 一种改性聚乙烯透气母粒及其制备方法 (Modified polyethylene breathable master batch and preparation method thereof ) 是由 晁磊 周如鸿 张俊武 于 2021-09-09 设计创作，主要内容包括：本发明涉及一种改性聚乙烯透气母粒及其制备方法,该母粒包括原料聚乙烯、石墨烯、滑石粉、碳酸钙和助剂,其制备方法先将石墨烯和多种助剂按一定顺序球磨后得到改性石墨烯粉末；再与聚乙烯、滑石粉、碳酸钙搅拌均匀,经熔融、挤出、切粒、烘干,即得改性聚乙烯透气母粒。本发明制备得到的改性聚乙烯透气母粒用于透气膜材料时具有透气、耐水以及拉伸强度高等优点。同时本发明的制备方法经济、环保,利于实现大规模连续化生产。(The invention relates to a modified polyethylene breathable master batch and a preparation method thereof, wherein the master batch comprises raw materials of polyethylene, graphene, talcum powder, calcium carbonate and auxiliaries; then evenly stirring the mixture with polyethylene, talcum powder and calcium carbonate, and obtaining the modified polyethylene breathable master batch through melting, extruding, granulating and drying. When the modified polyethylene breathable master batch prepared by the invention is used for breathable film materials, the modified polyethylene breathable master batch has the advantages of breathability, water resistance, high tensile strength and the like. Meanwhile, the preparation method is economical and environment-friendly, and is beneficial to realizing large-scale continuous production.)

1. The modified polyethylene breathable master batch is characterized by comprising the following components in parts by weight: 40-80 parts of polyethylene, 0.2-2 parts of graphene, 1-2 parts of talcum powder, 40-60 parts of calcium carbonate and 0.5-3 parts of auxiliary agent.

2. The modified polyethylene breathable masterbatch of claim 1, wherein the polyethylene is low density polyethylene with a density of 0.910-0.925 g/cm³。

3. The modified polyethylene breathable masterbatch according to claim 1, wherein the graphene has a transverse dimension of 0.4-50 μm and has less than 10 layers.

4. The modified polyethylene breathable masterbatch according to claim 1, wherein the calcium carbonate has a particle size distribution of 0.4 μm to 10 μm.

5. The modified polyethylene breathable masterbatch according to claim 1, wherein the auxiliary comprises, in parts by weight: 0.1-1 part of antioxidant, 0.2-1.5 parts of dispersant and 0.1-1 part of stabilizer.

6. The modified polyethylene breathable master batch according to claim 5, wherein the antioxidant is one or more of a phenolic antioxidant, a sulfur antioxidant, a phosphorus antioxidant or a natural antioxidant; the dispersing agent is one or more of calcium stearate, polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax or EVA wax; the stabilizer is one or more of an ultraviolet absorbent or a light stabilizer.

7. The preparation method of the modified polyethylene breathable master batch according to any one of claims 1 to 6, characterized by comprising the following steps:

(1) weighing graphene and a dispersing agent according to the weight parts, adding grinding beads for ball milling, adding an antioxidant and a stabilizing agent, continuing ball milling, and sieving to obtain modified graphene powder;

(2) weighing polyethylene, talcum powder and calcium carbonate according to the weight parts, and stirring; adding the modified graphene powder obtained in the step (1), and continuously stirring;

(3) and (3) adding the mixed material obtained in the step (2) into a double-screw extruder, and carrying out melting, extrusion, grain cutting and drying to obtain the modified polyethylene breathable master batch.

8. The preparation method of the modified polyethylene breathable master batch according to claim 7, wherein the material-bead ratio of the grinding beads in the step (1) is 5:3, and the ball milling time is 30-50 min each time.

9. The preparation method of the modified polyethylene breathable master batch according to claim 7, wherein the stirring temperature in the step (2) is 40-70 ℃, the stirring speed is 400-600 r/min, and the stirring time is 30-60 min each time.

10. The preparation method of the modified polyethylene breathable master batch according to claim 7, wherein the heating temperature zone for screw extrusion in the step (3) is as follows: 145-155 ℃ in the area 1, 155-165 ℃ in the area 2, 175-185 ℃ in the area 3, 185-195 ℃ in the area 4, 195-205 ℃ in the area 5, 200-210 ℃ in the area 6, 200-210 ℃ in the area 7, 200-210 ℃ in the area 8, 200 ℃ in the nose and 95-135 ℃ in the drying temperature.

Technical Field

The invention relates to the technical field of composite materials, and particularly relates to a modified polyethylene breathable master batch and a preparation method thereof.

Background

Polyethylene (PE) is a common engineering plastic and is widely used in various fields such as packaging materials, medical care, health, and automobiles. The air-permeable film prepared by casting or blow molding usually depends on added inorganic functional materials such as calcium carbonate and the like to stretch to form nano-micropores so as to achieve the effects of air (moisture) permeability and water resistance. In the stretching process, due to the insufficient ductility and other properties of polyethylene, pinholes, holes and even film breakage are easy to occur.

Graphene is a two-dimensional material with a number of excellent properties: the nano-sheet material has the advantages of ultrahigh specific surface area, extremely thin nano-sheet layer, stable chemical structure, good corrosion resistance and antibacterial property and excellent mechanical property. Has better application prospect in many fields.

Research shows that the graphene is added into a polymer material system in the form of nano filler, so that the polymer performance can be obviously improved (Xuanzheng. the performance research of a graphene oxide/polyvinyl alcohol composite membrane [ J ]. novel chemical material, 2017(04):47-49.), but the graphene is easy to agglomerate or stack in a dry state due to strong van der Waals force between graphene layers, and the comprehensive performance of the polymer material system is not improved. Therefore, how to better utilize the graphene modified polyethylene composite material is a technical problem which needs to be solved urgently in the field.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects of insufficient tensile strength and the like of the existing polyethylene breathable film and provides the modified polyethylene breathable master batch with good tensile strength, simple process, economy and environmental protection and the preparation method thereof.

The technical scheme for solving the technical problems is as follows:

the invention provides a modified polyethylene breathable master batch which is characterized by comprising the following components in parts by weight: 40-80 parts of polyethylene, 0.2-2 parts of graphene, 1-2 parts of talcum powder, 40-60 parts of calcium carbonate and 0.5-3 parts of auxiliary agent; preferably 90-105 parts of polyethylene, 0.5-1.5 parts of graphene, 1-1.5 parts of talcum powder, 40-55 parts of calcium carbonate and 0.5-2 parts of auxiliary agent;

further, the polyethylene is low-density polyethylene with the density of 0.910-0.925 g/cm³；

Further, the transverse size of the graphene is 0.4-50 microns, and the number of sheets is less than 10;

further, the particle size distribution of the calcium carbonate is 0.4-10 μm;

further, the auxiliary agent comprises the following components in parts by weight: 0.1-1 part of antioxidant, 0.2-1.5 parts of dispersant and 0.1-1 part of stabilizer; preferably 0.1-0.5 part of antioxidant, 0.2-1 part of dispersant and 0.1-0.5 part of stabilizer;

further, the antioxidant is one or more of a phenolic antioxidant, a sulfur antioxidant, a phosphorus antioxidant or a natural antioxidant; the dispersing agent is one or more of calcium stearate, polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax or EVA wax; the stabilizer is one or more of an ultraviolet absorbent or a light stabilizer;

the invention also provides a preparation method of the modified polyethylene breathable master batch, which is characterized by comprising the following steps:

(1) weighing graphene and a dispersing agent according to the weight parts, adding grinding beads for ball milling, adding an antioxidant and a stabilizing agent, continuing ball milling, and sieving to obtain modified graphene powder;

(2) weighing polyethylene, talcum powder and calcium carbonate according to the weight parts, and stirring; adding the modified graphene powder obtained in the step (1), and continuously stirring;

(3) adding the mixed material obtained in the step (2) into a double-screw extruder, and carrying out melting, extrusion, grain cutting and drying to obtain the modified polyethylene breathable master batch;

further, the material-to-bead ratio of the grinding beads in the step (1) is 5:3, and the ball milling time is 30-50 min each time; preferably, the ball milling time is 40min each time;

further, in the step (2), the stirring temperature is 40-70 ℃, the stirring speed is 400-600 r/min, and the stirring time is 30-60 min each time; preferably, the stirring temperature is 40 ℃, the stirring speed is 600r/min, and the stirring time is 30min each time;

further, the heating temperature zone for screw extrusion in the step (3) is as follows: 145-155 ℃ in the area 1, 155-165 ℃ in the area 2, 175-185 ℃ in the area 3, 185-195 ℃ in the area 4, 195-205 ℃ in the area 5, 200-210 ℃ in the area 6, 200-210 ℃ in the area 7, 200-210 ℃ in the area 8, 200 ℃ in the nose and 95-135 ℃ in the drying temperature.

The invention has the beneficial effects that: the modified polyethylene breathable master batch prepared by adding the modified graphene powder into polyethylene has good mechanical properties, and has the advantages of breathability, water resistance, high tensile strength and the like when used for preparing breathable film materials. Meanwhile, the preparation method is economical and environment-friendly, and is beneficial to realizing large-scale continuous production.

Detailed Description

The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.

Example 1:

weighing 1 part of graphene and 0.5 part of dispersing agent, adding the graphene and the dispersing agent into a ball milling dispersing tank, adding grinding beads, wherein the material bead ratio is 5:3, carrying out ball milling for 40min, weighing 0.2 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified graphene powder for later use.

46 parts of polyethylene, 1.5 parts of talcum powder and 43 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. And adding the screened modified graphene powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Example 2:

weighing 1.2 parts of graphene and 0.6 part of dispersing agent, adding into a ball milling dispersing tank, adding grinding beads with a bead ratio of 5:3, carrying out ball milling for 40min, weighing 0.2 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified graphene powder for later use.

50 parts of polyethylene, 1.5 parts of talcum powder and 48 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. And adding the screened modified graphene powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Example 3:

weighing 0.7 part of graphene and 0.4 part of dispersing agent, adding into a ball milling dispersing tank, adding grinding beads with a bead ratio of 5:3, carrying out ball milling for 40min, weighing 0.1 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified graphene powder for later use.

52 parts of polyethylene, 1 part of talcum powder and 40 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. And adding the screened modified graphene powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Example 4:

weighing 1.5 parts of graphene and 0.7 part of dispersing agent, adding into a ball milling dispersing tank, adding grinding beads with a bead ratio of 5:3, carrying out ball milling for 40min, weighing 0.2 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified graphene powder for later use.

53 parts of polyethylene, 1.5 parts of talcum powder and 54 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. And adding the screened modified graphene powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Comparative example 1:

weighing 0.5 part of dispersing agent, adding into a ball milling dispersing tank, adding grinding beads with a bead ratio of 5:3, ball milling for 40min, weighing 0.2 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified auxiliary agent powder for later use.

46 parts of polyethylene, 1.5 parts of talcum powder and 43 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. Adding the screened modification auxiliary agent powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Comparative example 2:

weighing 1 part of graphene and 0.5 part of dispersing agent, adding the graphene and the dispersing agent into a ball milling dispersing tank, adding grinding beads, wherein the material bead ratio is 5:3, carrying out ball milling for 40min, weighing 0.2 part of antioxidant and 0.2 part of stabilizing agent, continuing ball milling for 40min, and sieving the mixture to obtain modified graphene powder for later use.

80 parts of polyethylene, 1.5 parts of talcum powder and 30 parts of calcium carbonate are weighed and stirred in a stirring barrel at 40 ℃ for 30min at the rotating speed of 600 r/min. And adding the screened modified graphene powder, and continuously stirring and mixing for 30 min.

Putting the mixture into a double-screw extruder, and performing melt mixing extrusion, wherein the heating temperature zone for screw extrusion is as follows: 150 ℃ in the region 1, 160 ℃ in the region 2, 180 ℃ in the region 3, 190 ℃ in the region 4, 200 ℃ in the region 5, 205 ℃ in the region 6, 205 ℃ in the region 7, 205 ℃ in the region 8, 200 ℃ in the head, water-cooling the extruded material by a water tank, blowing the water out, drying the water by a fan, cutting the material into particles by a granulator, and drying the particles at 125 ℃ to obtain the modified polyethylene breathable master batch.

Test example:

the master batches obtained in examples 1-4 and comparative examples 1-2 were used to prepare breathable films for performance testing, and the results were as follows:

the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.