CN113354899A - Light micro-foaming polypropylene composite material and preparation method thereof - Google Patents
Light micro-foaming polypropylene composite material and preparation method thereof Download PDFInfo
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- 238000005187 foaming Methods 0.000 title claims abstract description 72
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 68
- -1 polypropylene Polymers 0.000 title claims abstract description 68
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title description 8
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 29
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 29
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 15
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 15
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 239000002667 nucleating agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 210000003850 cellular structure Anatomy 0.000 abstract description 5
- 238000005303 weighing Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
Abstract
The invention discloses a light micro-foaming polypropylene composite material which is characterized by comprising the following raw materials in parts by weight: 5-15 parts of high-concentration AC foaming master batch; 10-20 parts of ethylene propylene diene monomer; 70-80 parts of polypropylene; 1-4 parts of nano silicon dioxide; 0.4-1.2 parts of nano zinc oxide; 0.1-0.3 part of zinc stearate; the high-concentration AC foaming master batch consists of 15 parts by weight of azodicarbonamide and 85 parts by weight of low-density polyethylene; the method adopts an internal mixing blending mode, firstly melts the low-density polyethylene, then adds the azodicarbonamide to fully mix and shear into granules. The obtained product has a cellular structure with uniform structure, small size and high density, so that the quality of the product is reduced, the addition amount of raw materials is saved, and the product still maintains excellent mechanical properties under the condition of small consumption and low quality.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a light micro-foaming polypropylene composite material and a preparation method thereof.
Background
In recent years, microcellular polypropylene has been receiving attention from researchers. Compared with the common foaming plastic, the high-strength polyurethane foaming plastic has higher rigidity, chemical resistance and economic benefit. In particular its good thermal stability. Bringing more possibilities for its application. Meanwhile, the existence of the cellular structure inevitably improves the heat insulation, sound insulation and energy absorption capacity of the composite material. The polypropylene foam material is used for replacing unfoamed polypropylene or other foaming materials, so that the use of raw materials can be reduced, and the overall mass can be reduced to reduce the consumption of energy. The method endows the micro-foamed PP with great application potential in the fields of automobiles, buildings, aviation, industry and agriculture and the like.
Although PP has many advantages, it has a linear structure of internal molecules and a crystalline phase, and thus exhibits low melt strength, so that foaming properties are poor. In particular, at high temperatures, the molten PP does not have sufficient viscosity to encapsulate the gases generated during the foaming process, some of the gases are directly broken out, or they merge to form a macroporous structure, which is present in the material in the form of defects, seriously deteriorating its mechanical properties. For the foaming material, only if the generated foam holes are densely and uniformly distributed in the matrix, the foaming material has good mechanical properties while the quality of the material is reduced.
Disclosure of Invention
The invention aims to provide a micro-foaming polypropylene composite material and a preparation method thereof, wherein the material has a cellular structure with uniform structure, small size and high density, so that the quality of the material is reduced, the addition amount of raw materials is saved, and the material still maintains excellent mechanical properties under the condition of small consumption and low quality.
In order to achieve the purpose, the technical scheme is as follows:
a light micro-foaming polypropylene composite material is composed of the following raw materials in parts by weight:
5-15 parts of high-concentration AC foaming master batch;
10-20 parts of ethylene propylene diene monomer;
70-80 parts of polypropylene;
1-4 parts of heterogeneous nucleating agent nano silicon dioxide;
0.4-1.2 parts of nano zinc oxide;
0.1 to 0.3 portion of zinc stearate.
According to the scheme, the high-concentration AC foaming master batch consists of 15 parts by weight of azodicarbonamide and 85 parts by weight of low-density polyethylene; the method adopts an internal mixing blending mode, firstly melts the low-density polyethylene, then adds the azodicarbonamide for full mixing, and shears the mixture into granules.
According to the scheme, the molecular weight of the ethylene propylene diene monomer is 100000-135000, the molecular weight distribution index is 2.0-4.0, and the Mooney viscosity
Is 20-40.
According to the scheme, the crystallinity of the polypropylene is 40-60%, and the melt index is 5-15g/10min when the weight is 2.16 kg at 230 ℃.
According to the scheme, the purity of the nano silicon dioxide is more than 99%, and the particle size is less than 50 nm. The addition amount is 4 times of that of the nano zinc oxide.
According to the scheme, the purity of the nano zinc oxide is more than 99.5%, and the particle size is less than 50 nm.
The preparation method of the microcellular foamed polypropylene composite material comprises the following steps:
(1) fully and uniformly mixing the high-concentration AC foaming master batch, polypropylene, ethylene propylene diene monomer, heterogeneous nucleating agent nano silicon dioxide, nano zinc oxide and zinc stearate in proportion;
(2) carrying out melt blending on the obtained mixed material at the temperature of 165-180 ℃ by adopting a double-screw extruder, extruding and granulating to obtain pre-foamed master batch;
(3) filling the pre-foaming master batch into a mold, pressurizing for 5-10MPa at 185-195 ℃, maintaining the pressure for 3-5min, and then cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the ethylene propylene diene monomer to improve the melt strength of the polypropylene, and the addition of the ethylene propylene diene monomer can enhance the gas coating capability of the polypropylene in a molten state, influence the crystallization kinetics of the polypropylene and reduce the deterioration of cells. The chemical foaming agent adopts azodicarbonamide, and the foaming control mode is mainly used for adjusting the temperature in the foaming process. The nucleating agent is nano silicon dioxide, when a proper amount of inorganic nano particles are uniformly distributed in the matrix, the strengthening effect is achieved, a solid-melt two-phase interface can be formed, the tension at the heterogeneous interface is lowest, and a good environment is provided for bubble nucleation.
In the invention, the melt strength of the polypropylene is changed by mainly adjusting the addition of the ethylene propylene diene monomer, the gas coating capability of the polypropylene in a melting and converting state is improved, and the crystallization kinetics of the polypropylene is influenced to form more crystal nuclei, so that the nucleation of foam pores is promoted, the cell density of the foaming material is increased, and the cell size is reduced. With the increase of the addition of the ethylene propylene diene monomer, the diameter of the foam pores is reduced and then increased, the density of the foam pores is increased and then reduced, and the impact strength is greatly increased. The invention not only saves the addition of raw materials, but also obtains the microcellular foamed polypropylene composite material with uniform cellular structure, small size, higher density and good mechanical property.
In the invention, the preparation of the high-concentration AC foaming master batch has the following technical mechanism and effects: 1. the problem of flying of the AC powder can be effectively reduced, a large amount of AC master batches can be prepared, multiple production can be realized, the processes of weighing, mixing and the like of the AC powder are reduced, and the flying of dust can be effectively reduced. 2. Because the high-concentration particles are prepared firstly, the AC powder is dispersed in the LDPE for the first time, then the granular master batch is macroscopically mixed with the polypropylene and the ethylene propylene diene monomer, and finally an extruder is used for extrusion blending, the AC of the powder is well and uniformly dispersed in a foaming matrix in the three blending processes, and the foaming effect can be obviously improved. 3. The preparation of master batches in large quantities can also reduce the relative errors in the process of weighing the powder materials. The foaming agent is prepared into master batches, so that the master batches can be weighed more accurately during use, and the metering error is reduced. The LDPE is selected as the carrier of the master batch because the melting point of the LDPE is very low, and the LDPE cannot be decomposed in advance due to overhigh temperature when the AC foaming agent is mixed; and the LDPE has a structure with more branched chains in a molecular structure, and can also improve the melt strength of the polypropylene to promote the foaming effect.
Drawings
FIG. 1: microscopic topography of the foamed material obtained in example 2.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The invention provides a light micro-foaming polypropylene composite material which is prepared from the following raw materials in parts by weight:
5-15 parts of high-concentration AC foaming master batch; 10-20 parts of ethylene propylene diene monomer; 70-80 parts of polypropylene; 1-4 parts of heterogeneous nucleating agent nano silicon dioxide; 0.4-1.2 parts of nano zinc oxide; 0.1 to 0.3 portion of zinc stearate.
The preparation method of the microcellular foamed polypropylene composite material comprises the following steps:
mixing 15 weight portions of azodicarbonamide and 85 weight portions of low-density polyethylene; adopting an internal mixing blending mode, firstly melting low-density polyethylene, adding azodicarbonamide, fully mixing and shearing to obtain high-concentration AC foaming master batches;
fully and uniformly mixing the high-concentration AC foaming master batch, polypropylene, ethylene propylene diene monomer, heterogeneous nucleating agent nano silicon dioxide, nano zinc oxide and zinc stearate in proportion;
carrying out melt blending on the obtained mixed material at the temperature of 165-180 ℃ by adopting a double-screw extruder, extruding and granulating to obtain pre-foamed master batch;
filling the pre-foaming master batch into a mold, pressurizing for 5-10MPa at 185-195 ℃, maintaining the pressure for 3-5min, and then cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape.
In the example and comparative example composite formulations:
polypropylene is available from China petrochemical Thailand division under the trade name Primei 1100NK and has the density of 0.92g/cm3A melt index of 11g/10min at 230 ℃ under a weight of 2.16 kg;
the ethylene propylene diene monomer rubber is Dow 4820P, molecular weight is 10000, molecular weight distribution index is 2.0, Mooney viscosity
20, available from engineering plastics, Inc., Weilin, Guangdong;
the low density polyethylene has a trade name of MB9500, is available from Dongguan brand QI Plastic materials Co., Ltd, and has a density of 0.907g/cm3The melt flow index is 50g/10min at the temperature of 230 ℃;
the nano silicon dioxide has the purity of 99.5 percent and the particle size of 15 +/-5 nm, and is purchased from Shanghai Michelin Biochemical Co., Ltd;
azodicarbonamide available from alemba, technical grade;
both zinc oxide and zinc stearate were analytically pure and available from mclin ltd.
Example 1
Weighing 90 parts by weight of low-density polyethylene, placing the low-density polyethylene into an internal mixer, melting the low-density polyethylene in the internal mixer at 165 ℃ and the rotating speed of the internal mixer of 60r/min, then adding 10 parts of azodicarbonamide powder, carrying out internal mixing for 10 minutes, taking out the mixture, and shearing the mixture to obtain yellow high-concentration foaming master batches.
Weighing 85 parts by weight of polypropylene, 5 parts by weight of ethylene propylene diene monomer, 10 parts by weight of high-concentration foaming master batch, 2 parts by weight of nano silicon dioxide, 0.8 part by weight of nano zinc oxide and 0.2 part by weight of zinc stearate, mechanically blending and shaking uniformly, then putting into a double-screw extruder for melt blending, setting the temperature of the double-screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotating speed at 50r/min, and performing extrusion granulation to obtain granular pre-foaming master batch.
Filling the pre-foaming master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape, wherein the foaming performance is shown in Table 1.
Example 2
Weighing 85 parts by weight of low-density polyethylene, placing the low-density polyethylene into an internal mixer, melting the low-density polyethylene in the internal mixer at 165 ℃ and the rotating speed of the internal mixer of 60r/min, then adding 15 parts of azodicarbonamide powder, carrying out internal mixing for 10 minutes, taking out the mixture, and shearing the mixture to obtain yellow high-concentration foaming master batches.
Weighing 80 parts by weight of polypropylene, 10 parts by weight of ethylene propylene diene monomer, 10 parts by weight of high-concentration foaming master batch, 3 parts by weight of nano silicon dioxide, 0.8 part by weight of nano zinc oxide and 0.2 part by weight of zinc stearate, mechanically blending and shaking uniformly, then putting into a double screw extruder for melt blending, setting the temperature of the double screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotation speed at 50r/min, and performing extrusion granulation to obtain the granular pre-foaming master batch.
Filling the pre-foaming master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape, wherein the foaming performance is shown in Table 1. The scanning electron microscope cross-section of the micro-foamed polypropylene composite material obtained in this example is shown in FIG. 1.
Example 3
Weighing 95 parts by weight of low-density polyethylene, placing the low-density polyethylene into an internal mixer, melting the low-density polyethylene in the internal mixer at 165 ℃ and the rotating speed of the internal mixer of 60r/min, then adding 5 parts of azodicarbonamide powder, carrying out internal mixing for 10 minutes, taking out the mixture, and shearing the mixture to obtain yellow high-concentration foaming master batches.
Weighing 75 parts by weight of polypropylene, 15 parts by weight of ethylene propylene diene monomer, 10 parts by weight of high-concentration foaming master batch, 2 parts by weight of nano silicon dioxide, 0.4 part by weight of nano zinc oxide and 0.1 part by weight of zinc stearate, mechanically blending and shaking uniformly, then putting into a double screw extruder for melt blending, setting the temperature of the double screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotation speed at 50r/min, and performing extrusion granulation to obtain the granular pre-foaming master batch.
Filling the pre-foaming master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape, wherein the foaming performance is shown in Table 1.
Example 4
Weighing 85 parts by weight of low-density polyethylene, placing the low-density polyethylene into an internal mixer, melting the low-density polyethylene in the internal mixer at 165 ℃ and the rotating speed of the internal mixer of 60r/min, then adding 15 parts of azodicarbonamide powder, carrying out internal mixing for 10 minutes, taking out the mixture, and shearing the mixture to obtain yellow high-concentration foaming master batches.
Weighing 70 parts by weight of polypropylene, 20 parts by weight of ethylene propylene diene monomer, 10 parts by weight of high-concentration foaming master batch, 4 parts by weight of nano silicon dioxide, 0.4 part by weight of nano zinc oxide and 0.1 part by weight of zinc stearate, mechanically blending and shaking uniformly, then putting into a double screw extruder for melt blending, setting the temperature of the double screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotation speed at 50r/min, and performing extrusion granulation to obtain the granular pre-foaming master batch.
Filling the pre-foaming master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, and then cooling and demolding to obtain the micro-foaming polypropylene composite material with the specific shape. The foaming properties are shown in Table 1.
Example 5
Weighing 85 parts by weight of low-density polyethylene, placing the low-density polyethylene into an internal mixer, melting the low-density polyethylene in the internal mixer at 165 ℃ and the rotating speed of the internal mixer of 60r/min, then adding 15 parts of azodicarbonamide powder, carrying out internal mixing for 10 minutes, taking out the mixture, and shearing the mixture to obtain yellow high-concentration foaming master batches.
Weighing 65 parts by weight of polypropylene, 25 parts by weight of ethylene propylene diene monomer, 10 parts by weight of high-concentration foaming master batch, 3 parts by weight of nano silicon dioxide, 1.2 parts by weight of nano zinc oxide and 0.3 part by weight of zinc stearate, mechanically blending and shaking uniformly, then putting into a double screw extruder for melt blending, setting the temperature of the double screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotation speed at 50r/min, and performing extrusion granulation to obtain the granular pre-foaming master batch.
Filling the pre-foaming master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, cooling and demolding to obtain the micro-foaming polypropylene composite material with the specific shape, wherein the foaming performance of the micro-foaming polypropylene composite material is shown in Table 1.
Comparative example 1
An unfoamed polypropylene material, which is prepared by the following steps:
(1) weighing 100 parts by weight of polypropylene, 0.8 wt% of nano zinc oxide and 0.2 wt% of zinc stearate, mechanically mixing and shaking uniformly, then putting the mixture into a double-screw extruder for melt blending, setting the temperature of the double-screw extruder at 165-180 ℃, the feeding speed at 10r/min and the screw rotating speed at 50r/min, and carrying out extrusion granulation to obtain granular polypropylene master batches. (2) Filling the granular polypropylene master batch into a mold, pressurizing for 10MPa at 185-195 ℃, keeping the pressure for 5min, cooling and demolding to obtain the foamless polypropylene material with a specific shape. The foaming properties are shown in Table 1.
TABLE 1 relevant Properties of light foamed Polypropylene composite materials of examples 1-5 and comparative example 1
From the above detailed description of the embodiments of the present invention, it can be understood that the microcellular foamed polypropylene composite material prepared by the present invention has a cellular structure with a microscopic apparent density, which is greatly affected by the ethylene propylene diene monomer, which has a weaker branched chain than polypropylene and a long side chain, and has tighter entanglement among molecular chains, and the blending with polypropylene can increase the movement resistance of polypropylene molecular chain segments and effectively enhance the melt strength of polypropylene. Meanwhile, the ethylene propylene diene monomer rubber has good compatibility with polypropylene, can be uniformly dispersed in a polypropylene matrix, and can be used as a heterogeneous nucleation site to ensure that foam pores are denser and more uniform in dispersion. With increasing addition of ethylene propylene diene monomer, the apparent density of the microcellular foamed composite material shows a tendency to increase first and then decrease, and reaches a minimum value in example 2, which is 39.78% lower than the density of the unfoamed polypropylene in comparative example 1. It can be seen from the micro-topography of example 2 (attached FIG. 1) that the cells in example 2 are uniformly dispersed and dense. However, the reduction in density does not deteriorate the mechanical properties. The lowest density of example 2 is the highest in specific strength and impact due to the addition of the ethylene propylene diene monomer and the presence of the cells. Wherein the specific strength is improved by 23.41 percent compared with the comparative example 1, and the impact strength is improved by 55.4 percent. The ethylene propylene diene monomer rubber is beneficial to the foaming of polypropylene and can promote the improvement of partial mechanical property.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
Claims (7)
1. The light micro-foaming polypropylene composite material is characterized by comprising the following raw materials in parts by weight:
5-15 parts of high-concentration AC foaming master batch;
10-20 parts of ethylene propylene diene monomer;
70-80 parts of polypropylene;
1-4 parts of nano silicon dioxide;
0.4-1.2 parts of nano zinc oxide;
0.1 to 0.3 portion of zinc stearate.
2. The light-weight micro-foamed polypropylene composite material according to claim 1, wherein the high concentration AC foaming masterbatch is composed of 15 parts by weight of azodicarbonamide and 85 parts by weight of low density polyethylene; the method adopts an internal mixing blending mode, firstly melts the low-density polyethylene, then adds the azodicarbonamide to fully mix and shear into granules.
3. The light-weight micro-foamed polypropylene composite material as claimed in claim 1, wherein the molecular weight of the ethylene propylene diene monomer is 100000-135000, the molecular weight distribution index is 2.0-4.0, and the Mooney viscosity is 2.0-4.0
Is 20-40.
4. The light-weight micro-foamed polypropylene composite material according to claim 1, wherein the polypropylene has a crystallinity of 40% to 60% and a melt index of 5 to 15g/10min at 230 ℃ under a weight of 2.16 kg.
5. The light-weight micro-foamed polypropylene composite material according to claim 1, wherein the nano silica has a purity of more than 99% and a particle size of less than 50 nm.
6. The light-weight micro-foamed polypropylene composite material according to claim 1, wherein the nano zinc oxide has a purity of more than 99.5% and a particle size of less than 50 nm.
7. A method for preparing a microcellular foamed polypropylene composite material according to any one of claims 1 to 6, which comprises the steps of:
(1) fully and uniformly mixing the high-concentration AC foaming master batch, polypropylene, ethylene propylene diene monomer, heterogeneous nucleating agent nano silicon dioxide, nano zinc oxide and zinc stearate in proportion;
(2) carrying out melt blending on the obtained mixed material at the temperature of 165-180 ℃ by adopting a double-screw extruder, extruding and granulating to obtain pre-foamed master batch;
(3) filling the pre-foaming master batch into a mold, pressurizing for 5-10MPa at 185-195 ℃, maintaining the pressure for 3-5min, and then cooling and demolding to obtain the micro-foaming polypropylene composite material with a specific shape.
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| CN114891260A (en) * | 2022-04-22 | 2022-08-12 | 上海品磊塑胶有限公司 | Light plastic barrel and preparation method thereof |
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