CN113563630A - Preparation method and application of durable hydrophilic polypropylene foaming particles - Google Patents
Preparation method and application of durable hydrophilic polypropylene foaming particles Download PDFInfo
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- CN113563630A CN113563630A CN202110920266.8A CN202110920266A CN113563630A CN 113563630 A CN113563630 A CN 113563630A CN 202110920266 A CN202110920266 A CN 202110920266A CN 113563630 A CN113563630 A CN 113563630A
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- 239000002245 particle Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C08J9/16—Making expandable particles
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
- C08J9/12—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 physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
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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
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- C08J2203/06—CO2, N2 or noble gases
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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
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- C08J2203/08—Supercritical fluid
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- 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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- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
Abstract
The invention provides a preparation method of polypropylene foamed particles, which comprises the following steps of firstly, mixing polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic auxiliary agent and an antioxidant to obtain a mixture; and then blending and extruding the mixture obtained in the step and the supercritical fluid, and pelletizing to obtain the polypropylene foaming particles. The preparation process can modify and foam the polypropylene with less addition amount, and endow the polypropylene with special properties such as hydrophilicity, durability and porous foaming properties, thereby obviously improving the toughness and hydrophilicity of the polypropylene copolymer material, and being mainly applied to carriers of sewage treatment decomposition bacteria. Meanwhile, the preparation method provided by the invention has the advantages of simple production process, easy control, clean and environment-friendly whole process, and complete recycling of products, and is favorable for realizing industrial mass production and application.
Description
Technical Field
The invention belongs to the technical field of polypropylene foaming materials, relates to a preparation method and application of polypropylene foaming particles, and particularly relates to a preparation method of durable hydrophilic polypropylene foaming particles and application of the durable hydrophilic polypropylene foaming particles in a carrier material for sewage treatment.
Background
The foam plastic has the advantages of light weight, heat insulation, buffering, insulation, corrosion prevention, low price and the like, so the foam plastic is widely applied to daily necessities, packaging, industry, agriculture, transportation industry, military industry and aerospace industry, and the development of the foam plastic is very rapid since 20 th century and 90 th year in China, wherein the main varieties comprise three major types of Polyurethane (PU) flexible and rigid foam plastic, Polystyrene (PS) foam plastic and Polyethylene (PE) foam plastic. However, in the polyurethane foam, there is isocyanate residue harmful to human body during foaming, and the foamed material cannot be recycled. However, during the foaming process of Polystyrene (PS), chlorofluorocarbon or butane is usually used, which has adverse effects on the environment, and the products are difficult to degrade and easily form "white pollution", so the united nations environmental protection organization has decided to stop using PS foamed products. The rigidity of the cross-linked polyethylene foam is low, and the maximum service temperature is 80 ℃.
Polypropylene is a crystalline polymer with regular structure, is white waxy material, and is transparent and light in appearance. Has the chemical formula of (C3H6)nThe density is 0.89 to 0.91g/cm3The material is flammable, has a melting point of 165 ℃, is softened at about 155 ℃, and has a use temperature range of-30-140 ℃. Can resist corrosion of acid, alkali, salt solution and various organic solvents at the temperature of below 80 ℃, and can be decomposed at high temperature and under the action of oxidation. From the performance point of view, polypropylene (PP) is more rigid than Polyethylene (PE), and the chemical resistance is similar to PE; the glass transition temperature of the polypropylene is lower than room temperature, the impact resistance is superior to PS, and the polypropylene foam is an environment-friendly material; the polypropylene has higher heat distortion temperature and can be applied in some high-temperature fields. Expanded polypropylene is generally capable of withstanding high temperatures of 130 c, much higher than the maximum service temperature of 80 c for polyethylene foam. The closed cell structure makes the thermal conductivity of the cell structure not affected by moisture, so that the cell structure can be used as a heat preservation material; good low temperature characteristics, i.e.The performance is good at minus 30 ℃; the energy absorption, the PP foaming product has good energy absorption characteristic and excellent compression-resistant energy absorption performance, can be widely applied to an automobile bumper energy treatment system and other anti-collision energy absorption components, and has size and shape recovery stability, and the PP foaming product can quickly recover the original shape without permanent deformation after being subjected to multiple continuous impacts and flexural deformations; the product has the advantages of light weight, repeated use, good flexibility, difficult breakage, easy recycling, easy decomposition, no toxic and harmful components to human bodies, and no toxic substances generated by combustion; the PP foaming product is semi-hard formed, has moderate hardness and flexibility, does not scratch or bruise objects contacted with the PP foaming product, and has better surface protection. Therefore, the research and development of polypropylene foam have also become hot spots in recent years, and although polypropylene foam products have good performance and application prospects, the development difficulty of polypropylene foam is very high, related and industrializable core technologies exist in China, and some developed countries are under vigorous development and are used as green materials for replacing expanded polystyrene.
Therefore, how to find a suitable method to endow polypropylene materials with more characteristics, widen the application field of polypropylene foam materials, and deepen the application thereof has become one of the focuses of great attention of many research and development manufacturers and researchers.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polypropylene foamed particle and a preparation method thereof, and particularly to a preparation method of a durable hydrophilic polypropylene foamed particle.
The invention provides a preparation method of polypropylene foaming particles, which comprises the following steps:
1) mixing polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic additive and an antioxidant to obtain a mixture;
2) and (3) blending and extruding the mixture obtained in the step and the supercritical fluid, and pelletizing to obtain the polypropylene foaming particles.
Preferably, the preparation method comprises the following steps of counting the raw materials in parts by weight
Preferably, the melt index of the polypropylene is 0.5-10 g/10 min;
the density of the high-density polyethylene-octene copolymer elastomer is 0.857-0.880 g/cm3；
The hydrophilic auxiliary agent comprises one or more of talcum powder, glyceryl monostearate, polyethylene glycol, polyethylene oxide, polyvinyl alcohol and hydroxyethyl cellulose;
the antioxidant comprises one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 246, antioxidant 1098 and antioxidant 245.
Preferably, in the preparation method, one or more of the raw materials are dried raw materials;
the drying temperature is 40-100 ℃;
the drying time is 3-6 hours.
Preferably, the rotation speed of the mixing is 200-300 rpm;
the mixing time is 10-15 minutes;
the supercritical fluid comprises supercritical N2And/or supercritical CO2。
Preferably, the volume ratio of the supercritical fluid to the mixture is (0.05-0.1): 100, respectively;
the adding rate of the supercritical fluid is 0.001-0.002L/min;
the blending extrusion mode comprises twin-screw blending extrusion.
Preferably, the temperature of the blending extrusion is 190-220 ℃;
after the blending extrusion, releasing pressure and foaming at a neck ring die to obtain a polypropylene foaming brace;
the decompression pressure of the mouth mold for co-mixing extrusion is 2-4 Mpa;
the temperature of the neck ring mold for blending and extrusion is 220-240 ℃.
Preferably, the particle size of the foaming particles is 10-25 mm;
the foaming ratio of the polypropylene foaming particles is 1.5-3 times;
the polypropylene foamed particles comprise hydrophilic polypropylene foamed particles.
Preferably, the polypropylene foamed particles have a uniform cell distribution;
the cells are of a closed cell structure;
the diameter of the foam hole of the polypropylene foaming particle is 300-650 mu m.
The invention also provides application of the polypropylene foamed particles prepared by the preparation method in any one of the technical schemes in the aspect of carrier materials for sewage treatment.
The invention provides a preparation method of polypropylene foamed particles, which comprises the following steps of firstly, mixing polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic auxiliary agent and an antioxidant to obtain a mixture; and then blending and extruding the mixture obtained in the step and the supercritical fluid, and pelletizing to obtain the polypropylene foaming particles. Compared with the prior art, the invention is based on the research that the supercritical fluid (SCF, which refers to the fluid above the critical temperature and the critical pressure) can be used for preparing the polymer foaming material by utilizing the advantages of high diffusion rate, high solubility and the like of the supercritical fluid in the polymer because the viscosity and the diffusion coefficient are close to gas, and the density and the solvation capacity are close to liquid, and the supercritical fluid foaming technology is clean in the whole foaming process and can not pollute the environment and foaming products. Based on the above, the invention creatively provides a preparation method of specific polypropylene foaming particles, which can modify and foam the polypropylene foaming particles with a small addition amount, and endow the polypropylene foaming particles with special properties such as hydrophilicity, durability and porous foaming properties, thereby obviously improving the toughness and hydrophilicity of the polypropylene copolymer material. The hexagonal foaming particles obtained by the invention have the characteristics of wear resistance, hydrophilicity and porous structure, and can be mainly applied to carriers for decomposing bacteria in sewage treatment. Meanwhile, the preparation method provided by the invention has the advantages of simple production process, easy control, clean and environment-friendly whole process, complete recycling of products and customization of equipment, and is favorable for realizing industrial scale production and application.
Experimental results show that the preparation method provided by the invention is combined with a continuous extrusion foaming production process, continuous production of polypropylene particles can be realized, and the production efficiency is high. The diameter of the foam hole of the prepared foaming particle is 300-650 mu m, the foaming is 1.5-3 times, the surface hardness is high, and the Shore A hardness is 50-80 degrees; the hydrophilicity is good, and the surface infiltration time is less than 0.5 s; under the condition of low-speed mechanical stirring, the breaking rate is low, and the bacterial carrier material is excellent in performance.
Drawings
FIG. 1 is a photograph showing the appearance of polypropylene expanded beads prepared in the example of the present invention;
FIG. 2 is an electron microscope image of the cell structure of the internal section of the polypropylene foamed particle prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the purity requirements of analytical purity or the purity requirements of the polypropylene foaming material preparation field.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a preparation method of polypropylene foaming particles, which comprises the following steps:
1) mixing polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic additive and an antioxidant to obtain a mixture;
2) and (3) blending and extruding the mixture obtained in the step and the supercritical fluid, and pelletizing to obtain the polypropylene foaming particles.
The invention firstly mixes the polypropylene, the high-density polyethylene-octene copolymer elastomer, the hydrophilic additive and the antioxidant to obtain a mixture.
In the present invention, the polypropylene is preferably added in an amount of 50 to 80 parts by weight, more preferably 55 to 75 parts by weight, and still more preferably 60 to 70 parts by weight.
In the invention, the melt index of the polypropylene is preferably 0.5-10 g/10min, more preferably 2.5-8 g/10min, and more preferably 4-6 g/10 min. Specifically, the melt index was measured at 230 ℃ under a weight of 2.16 kg.
In the present invention, the high-density polyethylene-octene copolymer elastomer is preferably added in an amount of 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, and still more preferably 20 to 30 parts by weight.
In the present invention, the density of the high-density polyethylene-octene copolymer elastomer is preferably 0.857 to 0.880g/cm3More preferably 0.860 to 0.875g/cm3More preferably 0.865 to 0.870g/cm3。
In the present invention, the hydrophilic additive is preferably added in an amount of 3 to 5 parts by weight, more preferably 3.4 to 4.6 parts by weight, and still more preferably 3.8 to 4.2 parts by weight.
In the present invention, the hydrophilic auxiliary agent preferably includes one or more of talc, glyceryl monostearate, polyethylene glycol, polyethylene oxide, polyvinyl alcohol and hydroxyethyl cellulose, and more preferably talc, glyceryl monostearate, polyethylene glycol, polyethylene oxide, polyvinyl alcohol or hydroxyethyl cellulose.
In the present invention, the antioxidant is preferably added in an amount of 1 to 2 parts by weight, more preferably 1.2 to 1.8 parts by weight, and still more preferably 1.4 to 1.6 parts by weight.
In the present invention, the antioxidant preferably includes one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 246, antioxidant 1098 and antioxidant 245, and more preferably antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 246, antioxidant 1098 or antioxidant 245.
Specifically, the hydrophilic polypropylene foamed particles comprise the following main materials in percentage by weight:
more specifically, the polypropylene may be RS1684 from BASELL;
the high-density polyethylene-octene copolymer elastomer is medium petrochemical FMA 016;
the hydrophilic auxiliary agent can be 1000-3000 meshes of talcum powder;
the antioxidant may be antioxidant 1010 from basf.
In the present invention, in the production method, one or more of the raw materials are preferably dried raw materials, and more preferably, a plurality of the raw materials are preferably dried raw materials.
In the invention, the drying temperature is preferably 40-100 ℃, more preferably 50-90 ℃, and more preferably 60-80 ℃.
In the present invention, the drying time is preferably 3 to 6 hours, more preferably 3.5 to 5.5 hours, and still more preferably 4 to 5 hours.
In the invention, the rotation speed of the mixing is preferably 200-300 rpm, more preferably 220-280 rpm, and more preferably 240-260 rpm.
In the present invention, the mixing time is preferably 10 to 15 minutes, more preferably 11 to 14 minutes, and still more preferably 12 to 13 minutes.
The invention further blends and extrudes the mixture obtained in the step and the supercritical fluid, and then cuts the mixture into particles to obtain the polypropylene foaming particles.
In the present invention, the supercritical fluid preferably includes supercritical N2And/or supercritical CO2More preferably supercritical N2Or supercritical CO2。
In the present invention, the volume ratio of the supercritical fluid to the mixed material is preferably 0.05% to 0.1%, more preferably 0.06% to 0.09%, and more preferably 0.07% to 0.08%.
More specifically, in the present invention, the supercritical fluid is metered into the screw of the extruder by a differential pressure flow pump. The pressure of the supercritical fluid before the flow meter is preferably 8-12 MPa, more preferably 8.5-11.5 MPa, more preferably 9-11 MPa, and more preferably 9.5-10.5 MPa.
In the invention, the addition rate of the supercritical fluid is preferably 0.001-0.002L/min, more preferably 0.0012-0.0018L/min, and more preferably 0.0014-0.0016L/min.
In the invention, the blending extrusion mode preferably comprises screw machine blending extrusion, more preferably twin-screw blending extrusion, and more preferably a twin-screw extruder special for supercritical foaming.
In the invention, the temperature of the blending extrusion is preferably 190-220 ℃, more preferably 195-215 ℃, and more preferably 200-210 ℃.
In the invention, after the blending extrusion, the pressure is released and the foaming is carried out at a mouth die preferably to obtain the polypropylene foaming brace.
In the invention, the decompression pressure of the blending extrusion die is preferably 2-4Mpa, more preferably 2.4-3.6 Mpa,
in the invention, the temperature of the die for blending and extruding is preferably 220-240 ℃, more preferably 224-236 ℃, and more preferably 228-232 ℃.
In the present invention, after the blending extrusion, a foam strand is obtained. The diameter of the foaming material strip is preferably 10-25 mm. Preferably, the strands are cut to a length-to-diameter ratio of 1:1 to obtain expanded beads. The particle size of the foaming particles is preferably 10-25 mm in diameter, more preferably 13-22 mm in diameter, and more preferably 16-19 mm in diameter. Specifically, the shape of the extruder die according to the present invention is preferably hexagonal, and the extrusion die preferably includes 3 extrusion holes. More preferably, the diameter of the hole of the extrusion die is preferably 10-25 mm in a hexagonal star shape.
In the present invention, the expansion ratio of the polypropylene expanded beads is preferably 1.5 to 3 times, more preferably 1.8 to 2.7 times, and still more preferably 2.1 to 2.4 times.
In the present invention, the polypropylene expanded particles preferably include hydrophilic polypropylene expanded particles.
In the present invention, the polypropylene foamed particles preferably have a uniform cell distribution.
In the present invention, the cells are preferably of a closed cell structure.
In the invention, the diameter of the foam hole of the polypropylene foaming particle is preferably 300-650 μm, more preferably 350-600 μm, more preferably 400-550 μm, more preferably 450-500 μm.
The invention is a complete and refined integral preparation process, and better improves the performance of polypropylene foaming particles, and the preparation method of the durable hydrophilic polypropylene foaming particles provided by the steps can specifically comprise the following steps:
a) mixing foamed polypropylene resin and high-density polyethylene-octene copolymer elastomer material;
b) carrying out supercritical extrusion foaming on the mixed polypropylene by using a double-screw extruder;
c) the special hexagonal strip foaming strip is formed by controlling the pressure release of an extruder system and the design of a special opening die, and then the strip foaming strip is cut into hexagonal polypropylene particles with uniform size by a granulator.
Specifically, preferably, polypropylene and an antioxidant are respectively dried in a vacuum oven at 60-80 ℃ for 3-6 hours, and then are mixed in a mixer according to the proportion for 10-15 minutes; and adding the uniformly mixed materials into an extruder, foaming, bracing and granulating to obtain the durable hydrophilic polypropylene foamed particles.
More specifically, polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic assistant and an antioxidant are respectively dried in a vacuum drying oven at 40-100 ℃ for 3-6 hours, and are put into a high-speed mixer according to the proportion to be mixed for 10-15 minutes; feeding the uniformly mixed materials into an extruder in proportion through a double-screw blending extruder with supercritical fluid injection equipment, and performing supercritical extrusion foaming on the materials.
The overall temperature of the double-screw extruder is controlled to be 190-220 ℃, the temperature of the neck ring mold is controlled to be 220-240 ℃, carbon dioxide gas (with the purity of 99.9%) is injected through a booster pump, the dosage is 0.001-0.002L/min, and the pressure relief pressure of the neck ring mold is 2-4 MPa. The extrusion die contained 3 extrusion holes in the shape of a hexagon with a diameter of 1 cm.
Finally, the obtained foaming material strips are cut into particles, and the obtained hexagonal foaming particles have the characteristics of wear resistance, hydrophilicity and a porous structure, and are mainly used as carriers for decomposing bacteria in sewage treatment.
The whole process of the invention is clean and environment-friendly, and the product can be completely recycled and mainly used for the carrier effect of degrading bacteria in sewage treatment equipment.
The invention also provides application of the polypropylene foamed particles prepared by the preparation method in any one of the technical schemes in the aspect of carrier materials for sewage treatment.
The steps of the invention provide a preparation method of durable hydrophilic polypropylene foaming particles and application of the durable hydrophilic polypropylene foaming particles in the aspect of carrier materials for sewage treatment. The preparation method of the specific polypropylene foaming particles can modify and foam the polypropylene foaming particles under the condition of less adding amount, and endow the polypropylene foaming particles with special properties such as hydrophilicity, durability and porous foaming properties, thereby obviously improving the toughness and hydrophilicity of the polypropylene copolymer material. The hexagonal foaming particles obtained by the invention have the characteristics of wear resistance, hydrophilicity and porous structure, and can be mainly applied to carriers for decomposing bacteria in sewage treatment. Meanwhile, the preparation method provided by the invention has the advantages of simple production process, easy control, clean and environment-friendly whole process, complete recycling of products and customization of equipment, and is favorable for realizing industrial scale production and application.
Experimental results show that the preparation method provided by the invention is combined with a continuous extrusion foaming production process, continuous production of polypropylene particles can be realized, and the production efficiency is high. The diameter of the foam hole of the prepared foaming particle is 300-650 mu m, the foaming is 1.5-3 times, the surface hardness is high, and the Shore A hardness is 50-80 degrees; the hydrophilicity is good, and the surface infiltration time is less than 0.5 s; under the condition of low-speed mechanical stirring, the breaking rate is low, and the bacterial carrier material is excellent in performance.
For further illustration of the present invention, the following will describe the preparation method and application of the polypropylene expanded beads provided by the present invention in detail with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Respectively drying the polypropylene RS1684 and the antioxidant in a vacuum oven at 60-80 ℃ for 3-6 hours, and then mixing the components in a proportion of 50: 40 polypropylene and high density polyethylene-octene copolymer elastomer were mixed in a mixer for 10-15 minutes.
Extruding and foaming the mixed materials by a double-screw extruder, adding 3% of hydrophilic auxiliary agent and 1% of antioxidant, controlling the overall temperature of the screw to be 190-220 ℃, controlling the temperature of an extrusion opening die to be 220-240 ℃, adding a trace amount of carbon dioxide foaming agent by a booster pump, wherein the dosage is 0.001-0.002L/min, and the pressure relief pressure of the opening die is 2-4MPa, thus preparing the foaming strip.
Cutting the foaming strips at a constant speed by a granulator to obtain hexagonal porous foaming particles with the diameter of 1.0-2.5 cm. The pore diameter of the large pore is 450-530 μm, and the foaming ratio is 3 times.
The polypropylene expanded particles prepared in example 1 of the present invention were characterized.
Referring to fig. 1, fig. 1 is a photograph showing the appearance of polypropylene expanded particles prepared according to an example of the present invention.
Referring to fig. 2, fig. 2 is an electron microscope image of the cell structure of the internal section of the polypropylene foamed particle prepared in example 1 of the present invention.
Example 2
Respectively drying the polypropylene RS1684 and the antioxidant in a vacuum oven at 60-80 ℃ for 3-6 hours, and then mixing the components in a proportion of 60: 40 polypropylene and high density polyethylene-octene copolymer elastomer were mixed in a mixer for 10-15 minutes.
Extruding and foaming the mixed materials by a double-screw extruder, adding 4% of hydrophilic auxiliary agent and 1.5% of antioxidant, controlling the overall temperature of the screw to be 190-220 ℃, controlling the temperature of an extrusion opening die to be 220-240 ℃, adding a trace amount of carbon dioxide foaming agent by a booster pump, wherein the dosage is 0.001-0.002L/min, and the pressure relief pressure of the opening die is 2-4MPa, thus preparing the foaming strip.
Cutting the foaming strips at a constant speed by a granulator to obtain hexagonal porous foaming particles with the diameter of 1.0-2.5cm, wherein the pore diameter of the large pores is 300-500 mu m, and the foaming ratio is 2 times.
Example 3
Respectively drying the polypropylene RS1684 and the antioxidant in a vacuum oven at 60-80 ℃ for 3-6 hours, and then mixing the components in a proportion of 80: 20 polypropylene and high density polyethylene-octene copolymer elastomer were mixed in a mixer for 10-15 minutes.
Extruding and foaming the mixed materials by a double-screw extruder, adding 5% of hydrophilic auxiliary agent and 2% of antioxidant, controlling the overall temperature of the screw to be 190-220 ℃, controlling the temperature of an extrusion opening die to be 220-240 ℃, adding a trace amount of carbon dioxide foaming agent by a booster pump, wherein the dosage is 0.001-0.002L/min, and the pressure relief pressure of the opening die is 2-4MPa, thus preparing the foaming strip.
Cutting the foaming strips at a constant speed by a granulator to obtain hexagonal porous foaming particles with the diameter of 1.0-2.5cm, wherein the pore diameter of the large pores is 200-400 mu m, and the foaming ratio is 1.5 times.
The performance of the durable hydrophilic polypropylene foamed particles prepared in the embodiments 1 to 3 of the invention is tested.
Referring to table 1, table 1 shows the performance test results of the polypropylene foamed particles prepared according to the present invention.
TABLE 1
| Examples | Surface wetting time/s | 5d breakage% | 10d breakage% | 20d breakage% | Shore A/° |
| Example 1 | 0.1 | 0 | 3 | 5 | 50 |
| Example 2 | 0.2 | 0 | 2 | 4 | 65 |
| Example 3 | 0.5 | 0 | 1 | 2 | 80 |
Note: the surface infiltration time refers to the calculated bead flattening time of the water drop on the particle section. The stirring speed was 10 rpm.
The foregoing detailed description of the method for making durable hydrophilic polypropylene expanded beads of the present invention and the use thereof in a carrier material for wastewater treatment applications has been presented with specific examples to illustrate the principles and embodiments of the present invention, which are intended to facilitate an understanding of the methods of the present invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The preparation method of the polypropylene foaming particles is characterized by comprising the following steps:
1) mixing polypropylene, a high-density polyethylene-octene copolymer elastomer, a hydrophilic additive and an antioxidant to obtain a mixture;
2) and (3) blending and extruding the mixture obtained in the step and the supercritical fluid, and pelletizing to obtain the polypropylene foaming particles.
2. The preparation method according to claim 1, wherein the preparation method comprises the following steps of counting the mass parts of the raw materials
3. The preparation method according to claim 2, wherein the melt index of the polypropylene is 0.5 to 10g/10 min;
the density of the high-density polyethylene-octene copolymer elastomer is 0.857-0.880 g/cm3；
The hydrophilic auxiliary agent comprises one or more of talcum powder, glyceryl monostearate, polyethylene glycol, polyethylene oxide, polyvinyl alcohol and hydroxyethyl cellulose;
the antioxidant comprises one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 246, antioxidant 1098 and antioxidant 245.
4. The method according to claim 1, wherein one or more of the raw materials are dried raw materials;
the drying temperature is 40-100 ℃;
the drying time is 3-6 hours.
5. The method according to claim 1, wherein the mixing is performed at a rotation speed of 200 to 300 rpm;
the mixing time is 10-15 minutes;
the supercritical fluid comprises supercritical N2And/or supercritical CO2。
6. The preparation method according to claim 1, wherein the volume ratio of the supercritical fluid to the mixture is (0.05-0.1): 100, respectively;
the adding rate of the supercritical fluid is 0.001-0.002L/min;
the blending extrusion mode comprises twin-screw blending extrusion.
7. The preparation method of claim 1, wherein the temperature of the blending extrusion is 190-220 ℃;
after the blending extrusion, releasing pressure and foaming at a neck ring die to obtain a polypropylene foaming brace;
the decompression pressure of the mouth mold for co-mixing extrusion is 2-4 Mpa;
the temperature of the neck ring mold for blending and extrusion is 220-240 ℃.
8. The method according to claim 1, wherein the expanded beads have a particle diameter of 10 to 25 mm;
the foaming ratio of the polypropylene foaming particles is 1.5-3 times;
the polypropylene foamed particles comprise hydrophilic polypropylene foamed particles.
9. The production method according to claim 1, wherein the polypropylene foamed particles have a uniform cell distribution;
the cells are of a closed cell structure;
the diameter of the foam hole of the polypropylene foaming particle is 300-650 mu m.
10. Use of the polypropylene foamed particles prepared by the preparation method of any one of claims 1 to 9 in the aspect of carrier materials for sewage treatment.
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