CN112080067A - High-filling filler modified polyolefin composite material and preparation method and application thereof - Google Patents
High-filling filler modified polyolefin composite material and preparation method and application thereof Download PDFInfo
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- CN112080067A CN112080067A CN202010870724.7A CN202010870724A CN112080067A CN 112080067 A CN112080067 A CN 112080067A CN 202010870724 A CN202010870724 A CN 202010870724A CN 112080067 A CN112080067 A CN 112080067A
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000000945 filler Substances 0.000 title claims abstract description 68
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000011049 filling Methods 0.000 title claims description 37
- 239000000843 powder Substances 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- 239000004743 Polypropylene Substances 0.000 claims description 35
- 229920001155 polypropylene Polymers 0.000 claims description 35
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920000609 methyl cellulose Polymers 0.000 claims description 10
- 239000001923 methylcellulose Substances 0.000 claims description 10
- 235000010981 methylcellulose Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001046 Nanocellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- -1 polypropylene Polymers 0.000 description 32
- 229920003023 plastic Polymers 0.000 description 30
- 239000004033 plastic Substances 0.000 description 30
- 238000012545 processing Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 238000009863 impact test Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
- C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92619—Diameter or circumference
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of preparation of modified composite materials, and particularly relates to a high-filling-filler modified polyolefin composite material as well as a preparation method and application thereof. Mixing and uniformly stirring powder and a dispersant aqueous solution to obtain powder slurry; the primary extruder is a double-screw extruder, the polyolefin resin is fed from a main feeding port of the primary extruder, and the powder slurry is pressed in a middle plasticizing area of the primary extruder; the secondary extruder is a double-screw extruder and is positioned below the primary extruder, and the length-diameter ratio of screws is more than 48: 1; and enabling the composite material melt extruded by the primary extruder to flow into a main feeding port of the secondary extruder for blanking, and performing melt mixing extrusion, cooling, drying and grain cutting to obtain the high-filling-filler modified polyolefin composite material. The invention adopts a two-stage extrusion aqueous solution dispersion technology to be beneficial to the dispersion of high-filling-quantity powder in the polyolefin material, and the modified material has excellent physical and mechanical properties, simple manufacturing method and excellent material properties.
Description
Technical Field
The invention belongs to the technical field of preparation of modified composite materials, and particularly relates to a high-filling-filler modified polyolefin composite material as well as a preparation method and application thereof.
Background
Polyolefin is a common plastic material, has the characteristics of wide processing conditions, high processing stability and relatively low price, and is a common plastic material in daily life. By adding the inorganic powder into the polyolefin plastic, the performance of the plastic material can be improved, the crystallization can be accelerated, the heat resistance can be improved, and the cost can be effectively reduced, so that the polyolefin plastic is the most widely applied plastic in the current plastic products. The addition amount of the filler in the polyolefin plastic is obviously influenced by processing limitation, and the influence of a large amount of powder filling on the properties such as the fluidity, the strength and the like of a melt is obvious, so that high-concentration filling is difficult to realize through twin-screw extrusion.
In order to add a large amount of fillers into polyolefin, the main technical methods at present include a plurality of methods, one is to use low molecular weight resin to wrap powder to prepare master batch, and to add the master batch to improve dispersibility during processing, such as patent CN201810647628.9, but the adding concentration of the powder is obviously limited by the concentration limit of the fillers in the master batch; secondly, high-fluidity resin is used for matching, such as patents CN201611212433.9 and CN201811444777.1, but the high-fluidity resin is often low in molecular weight and has certain negative effects on heat resistance, strength and the like of the material; thirdly, design dedicated basic unit, can effectively improve filling efficiency through improving screw rod dispersion effect and shear strength, like patent CN201610910456.0, but this kind of equipment often belongs to professional equipment, and manufacturing cost is high, and the commonality is poor.
Of course, the processing is assisted in the polymer melt by means of a certain medium, and a certain dispersing effect can also be produced by generating a multidimensional unsteady force field. For example, patent CN200910057463.0 mentions co-extrusion of polypropylene and carbon nanotube dispersion liquid grafted with silane coupling agent, and utilizes hydrolysis of silane end group to realize cross-linking dispersion, but actually this kneading process is completely random, and cross-linking is also random, and the dispersion of powder in melt cannot be controlled. Patent CN201420045127.0 proposes an apparatus for preparing polymer nanocomposite by using nano aqueous dispersion liquid to assist in mixing extrusion and injection molding, wherein the use of nano powder aqueous dispersion liquid increases the pressure in the barrel due to the expansion effect and lubrication effect of water vapor, greatly reduces the dispersibility of the screw, and simultaneously the nano fluid itself has extremely low solid content, thus the effect of high filling cannot be achieved at all.
Based on the above, the polyolefin composite material filled with high filler still has a great problem in production and manufacturing, and it is difficult to obtain the high-filled polyolefin composite material on the premise of ensuring the physical properties of the material. The development of a simple and efficient extrusion method, and the realization of the uniform dispersion of high-quality-part powder in polyolefin becomes an important development direction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a high-filling filler modified polyolefin composite material.
The invention also aims to provide the high-filling filler modified polyolefin composite material prepared by the preparation method.
Still another object of the present invention is to provide the use of the highly filled filler modified polyolefin composite described above.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-filling filler modified polyolefin composite material comprises the following steps:
(1) mixing the powder with a dispersant aqueous solution and uniformly stirring to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, polyolefin resin is fed from a main feeding port of the primary extruder, and the powder slurry prepared in the step (1) is pressed in a middle plasticizing area of the primary extruder at a constant pump speed, wherein the pump pressure ratio is 1.01-1.05; the exhaust port is arranged at the tail part of the first-stage extruder and is removed in vacuum;
(3) the secondary extruder is a double-screw extruder and is positioned below the primary extruder, and the length-diameter ratio of screws is more than 48: 1; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder for blanking, arranging an exhaust port in the middle of the secondary extruder, and removing by vacuum; carrying out melt mixing extrusion, cooling, drying and grain cutting to obtain the high-filling filler modified polyolefin composite material;
the powder in the step (1) is preferably at least one of organic powder and inorganic powder, wherein the particle size of the powder is preferably 800-1250 meshes;
the organic powder is preferably at least one of nano cellulose, eluting wood fiber and the like;
the inorganic powder is preferably at least one of common inorganic powder for plastic processing, such as calcium carbonate, wollastonite, silica, talc, mica powder, carbon black and the like;
the dispersant in the step (1) is at least one of methyl cellulose, ethyl cellulose, isopropyl cellulose and polyethylene oxide;
the mass ratio of the powder to the dispersing agent in the powder slurry in the step (1) is (70-200): 1;
the mass fraction of the dispersant water solution in the step (1) is preferably 5-30%;
the mass fraction of the dispersant water solution in the step (1) is further preferably 10-20%;
uniformly mixing and stirring the mixture in the step (1), preferably mixing and fully stirring the mixture at room temperature for 5 to 24 hours;
mixing and stirring uniformly in the step (1), and further preferably mixing and stirring fully at room temperature for 12 hours;
the polyolefin resin in the step (2) is at least one of polyolefin materials such as high-density polyethylene, low-density polyethylene, homo-polypropylene, co-polypropylene, metallocene polyolefin, polyolefin elastomer, ethylene and long-chain olefin copolymer, ethylene and cyclic olefin copolymer, polybutene-1, polytrimethyl-pentene, polytetramethyl-pentene, polyethylene-vinyl alcohol copolymer, polyethylene-vinyl acetate copolymer and the like;
the method for pumping the powder slurry in the step (2) is preferably as follows:
pressing the powder slurry prepared in the step (1) into a middle plasticizing area of the primary extruder through a liquid metering pump at a constant pump speed;
the diameter of the screw of the primary extruder in the step (2) is preferably 35mm, the length-diameter ratio of the screw is preferably 30:1, and a double-cone homodromous screw is selected;
the diameter of a screw of the secondary extruder in the step (3) is preferably 35mm, the length-diameter ratio of the screw is preferably (48-54): 1, and a bi-flat reverse screw is selected;
the high-filling filler modified polyolefin composite material is prepared by the preparation method;
the high-filling filler modified polyolefin composite material is applied to the fields of household appliance shells, daily necessities, automobile materials and the like;
compared with the prior art, the invention has the following advantages and effects:
(1) the high-filling filler modified polyolefin composite material is prepared by adopting a two-stage extruder, wherein the pumping ratio is limited to be 1.01-1.05 in the first-stage extruder so as to prevent water-stopping colloid from returning to a pump; the secondary extruder is a double-screw extruder with the length-diameter ratio of more than 48:1, so that the uniform dispersion of the nano-filler in the polyolefin resin melt can be ensured.
(2) Compared with the mixing of solid powder and molten resin, the invention prepares the powder into liquid slurry, and simultaneously is supplemented with proper dispersant to be mixed with the molten resin more uniformly.
(3) The invention obtains the high-quality powder filled polyolefin nano composite material (the mass fraction of the filler can reach 50-70%), and can obtain the wide-range polyolefin composite material by adjusting the mass fraction of the powder in the powder dispersion liquid.
(4) The high-filling filler modified polyolefin composite material provided by the invention has excellent mechanical properties and excellent processing properties.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the examples, the particle size of calcium carbonate is 800 mesh;
the present invention will now be described in further detail by taking the preparation method of the highly filled calcium carbonate/polypropylene composite material as an example.
Example 1
(1) Mixing calcium carbonate serving as a filler and methylcellulose serving as a dispersing agent at room temperature, and stirring for 12 hours until the mixture is uniform, wherein the mass ratio of the calcium carbonate to the methylcellulose is 200:1, so as to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; feeding polypropylene resin (with the melt index of 3g/10min) from a main feeding port of a primary extruder, and pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the primary extruder at a constant pump speed by using a liquid metering pump, wherein the pump pressure ratio is maintained at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(3) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; in order to ensure the uniform dispersion of the nano-filler, the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; and the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion.
The filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 70%, the melt flow rate is 2.7g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is 124 ℃ according to the test standard GB/T1633 for the heat distortion temperature of plastics.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 30:70, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the performance of the polypropylene composite material is determined according to the plastic tensile test standard GB/T1040-1992 and the plastic impact test standard GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 26.7MPa, the elongation at break is 95.0 percent, and the impact strength is 8.7KJ/m2。
Example 2
(1) Mixing calcium carbonate serving as a filler and methylcellulose serving as a dispersing agent at room temperature, and stirring for 12 hours until the mixture is uniform, wherein the mass ratio of the calcium carbonate to the methylcellulose is 70:1, so as to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; feeding polypropylene resin (with the melt index of 6g/10min) from a main feeding port of a primary extruder, and pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the primary extruder at a constant pump speed by using a liquid metering pump, wherein the pump pressure ratio is maintained at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(3) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; in order to ensure the uniform dispersion of the nano-filler, the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; and the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion.
The filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 50%, the melt flow rate is 4.7g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is 118 ℃ measured according to the plastic heat distortion temperature test standard GB/T1633.
The high-filling filler modified polyolefin composite material prepared by the embodiment is injected into a standard tensile and impact sample at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃. And the properties of the composite were determined according to the Plastic tensile test Standard GB/T1040-1992 and the Plastic impact test Standard GB/T1843-.
The performance test results of the highly filled filler modified polyolefin composite material prepared in this example are as follows: the tensile strength is 27.8MPa, the elongation at break is 115.0 percent, and the impact strength is 11.7KJ/m2。
Example 3
(1) Mixing calcium carbonate serving as a filler and methylcellulose serving as a dispersing agent at room temperature, and stirring for 12 hours until the mixture is uniform, wherein the mass ratio of the calcium carbonate to the methylcellulose is 150:1, so as to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; feeding polypropylene resin (with the melt index of 10g/10min) from a main feeding port of a primary extruder, and pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the primary extruder at a constant pump speed by using a liquid metering pump, wherein the pump pressure ratio is maintained at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(3) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; in order to ensure the uniform dispersion of the nano-filler, the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion;
the filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 63 percent, the melt flow rate is 9.3g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is 118 ℃ measured according to the plastic heat distortion temperature test standard GB/T1633.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 20:80, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the performance of the polypropylene composite material is determined according to the plastic tensile test standard GB/T1040-1992 and the plastic impact test standard GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 27.8MPa, the elongation at break is 105.0 percent, and the impact strength is 10.2KJ/m2。
Comparative example 1 (polyvinyl alcohol as dispersant)
(1) Mixing calcium carbonate serving as a filler and polyvinyl alcohol serving as a dispersing agent with a polyvinyl alcohol aqueous solution with the mass fraction of 5% at room temperature, and stirring for 12 hours until the mixture is uniform, wherein the mass ratio of the calcium carbonate to the polyvinyl alcohol is 150:1, so as to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; feeding polypropylene resin (with the melt index of 10g/10min) from a main feeding port of a primary extruder, and pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the primary extruder at a constant pump speed by using a liquid metering pump, wherein the pump pressure ratio is maintained at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(3) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; in order to ensure the uniform dispersion of the nano-filler, the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion;
the filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 63 percent, the melt flow rate is 4g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is determined to be 98 ℃ according to the test standard GB/T1633 of the heat distortion temperature of the plastic.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 20:80, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the performance of the polypropylene composite material is determined according to the plastic tensile test standard GB/T1040-1992 and the plastic impact test standard GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 13.8MPa, the elongation at break is 55.0 percent, and the impact strength is 5.2KJ/m2。
COMPARATIVE EXAMPLE 2 (Using a first extruder)
(1) Mixing calcium carbonate serving as a filler and methylcellulose serving as a dispersing agent at room temperature, and stirring for 12 hours until the mixture is uniform, wherein the mass ratio of the calcium carbonate to the methylcellulose is 150:1, so as to obtain powder slurry;
(2) the extruder is a double-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 48:1, and the screw is a double-flat reverse screw; feeding polypropylene resin (with the melt index of 10g/10min) from a main feeding port of an extruder, pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the extruder at a constant pump speed by using a liquid metering pump, and maintaining the pump pressure ratio at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; setting the temperature of the extruder to 190/190/200/200/205/205 ℃ according to processing, setting an exhaust port at the tail part of the extruder, and selecting a vacuum pump for vacuum removal; and cooling, drying and granulating after extrusion to obtain the high-filling filler modified polyolefin composite material.
The filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 63 percent, the melt flow rate is 4g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is 102 ℃ measured according to the plastic heat distortion temperature test standard GB/T1633.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 20:80, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the properties of the polypropylene composite were determined according to the standards for plastic tensile testing GB/T1040-1992 and for plastic impact testing GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 16.3MPa, the elongation at break is 62.0 percent, and the impact strength is 6.3KJ/m2。
COMPARATIVE EXAMPLE 3 optional dispersant
(1) Calcium carbonate is used as a filler, and is mixed with water at room temperature and stirred for 12 hours until the mixture is uniform, so that powder slurry is obtained, wherein the content of the calcium carbonate is the same as that in the embodiment 3;
(2) the primary extruder is a single-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; feeding polypropylene resin (with the melt index of 10g/10min) from a main feeding port of a primary extruder, and pressing the powder slurry prepared in the step (1) into a plasticizing area in the middle of the primary extruder at a constant pump speed by using a liquid metering pump, wherein the pump pressure ratio is maintained at 1.01-1.05 to prevent water-stopping colloid from returning to a pump; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(3) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; in order to ensure the uniform dispersion of the nano-filler, the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion;
the filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 63 percent, the melt flow rate is 7.5g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is determined to be 98 ℃ according to the test standard GB/T1633 of the heat distortion temperature of the plastic.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 20:80, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the performance of the polypropylene composite material is determined according to the plastic tensile test standard GB/T1040-1992 and the plastic impact test standard GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 15.9MPa, the elongation at break is 65.0 percent, and the impact strength is 9.2KJ/m2。
Comparative example 4 (calcium carbonate solid filler directly melt-mixed with resin)
(1) The primary extruder is a single-screw extruder, wherein the diameter of a screw is 35mm, the length-diameter ratio of the screw is 30:1, and the primary extruder is a double-cone homodromous screw; polypropylene resin (melt index 10g/10min) is fed from the main feeding port of the primary extruder, and calcium carbonate powder (the same amount as that in example 3) is added from the side feeding port; the temperature of the primary extruder is set to be 150/190/190/200/220 ℃ according to processing, the exhaust port is arranged at the tail part of the primary extruder, and a vacuum pump is selected for vacuum removal;
(2) the secondary extruder is a double-screw extruder and is arranged below the primary extruder; the screw diameter of the secondary extruder is 35mm, the length-diameter ratio of the screw is 48:1, and the secondary extruder is a bi-flat reverse screw; enabling the composite material melt extruded by the primary extruder in the step (1) to flow into a main feeding port of a secondary extruder, wherein the temperature of the secondary extruder is set to be 190/190/200/200/205/205 ℃ according to processing; the exhaust port is arranged in the middle of the secondary extruder, a vacuum pump is selected for vacuum removal, and the high-filling filler modified polyolefin composite material is obtained after cooling, drying and grain cutting after extrusion;
the filler filling mass of the high-filling filler modified polyolefin composite material prepared by the embodiment is 63 percent, the melt flow rate is 3.2g/10min, the test condition is 230 ℃, and the load is 2.16 Kg. The heat distortion temperature of the composite material is 85 ℃ measured according to the plastic heat distortion temperature test standard GB/T1633.
The pure polypropylene resin and the high-filling-material-modified polyolefin composite material prepared in the embodiment are mixed according to the mass ratio of 20:80, and then a standard tensile sample and an impact sample are injected at the injection temperature of 180 ℃/190 ℃/200 ℃/210 ℃ to obtain the polypropylene composite material. And the performance of the polypropylene composite material is determined according to the plastic tensile test standard GB/T1040-1992 and the plastic impact test standard GB/T1843-.
The performance measurement results of the polypropylene composite material prepared by the method are as follows: the tensile strength is 7.9MPa, the elongation at break is 42.0 percent, and the impact strength is 5.2KJ/m2。
From the test results of the examples and the comparative examples, the single-stage extrusion can not realize sufficient dispersion of the filler slurry, the dispersing effect of the filler is obviously affected by adding no dispersing agent, the dispersing agent is not properly selected, and the performance of the composite material is possibly worse; such as complete loss of mechanical properties when added directly to the powder composite. The two-stage extrusion aqueous solution dispersion technology provided by the invention is beneficial to the dispersion of high-filling-quantity powder in a polyolefin material, and enables the modified material to have excellent physical and mechanical properties, and the preparation method is simple and the material properties are excellent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-filling filler modified polyolefin composite material is characterized by comprising the following steps:
(1) mixing the powder with a dispersant aqueous solution and uniformly stirring to obtain powder slurry;
(2) the primary extruder is a double-screw extruder, polyolefin resin is fed from a main feeding port of the primary extruder, and the powder slurry prepared in the step (1) is pressed in a middle plasticizing area of the primary extruder at a constant pump speed, wherein the pump pressure ratio is 1.01-1.05; the exhaust port is arranged at the tail part of the first-stage extruder and is removed in vacuum;
(3) the secondary extruder is a double-screw extruder and is positioned below the primary extruder, and the length-diameter ratio of screws is more than 48: 1; enabling the composite material melt extruded by the primary extruder in the step (2) to flow into a main feeding port of a secondary extruder for blanking, arranging an exhaust port in the middle of the secondary extruder, and removing by vacuum; and carrying out melt mixing extrusion, cooling, drying and grain cutting to obtain the high-filling-filler modified polyolefin composite material.
2. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the powder in the step (1) is at least one of organic powder and inorganic powder, wherein the particle size of the powder is 800-1250 meshes.
3. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the organic powder is at least one of nano cellulose and eluting wood fiber;
the inorganic powder is at least one of calcium carbonate, wollastonite, silicon dioxide, talc, mica powder and carbon black.
4. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the dispersant in the step (1) is at least one of methyl cellulose, ethyl cellulose, isopropyl cellulose and polyethylene oxide.
5. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the mass ratio of the powder to the dispersing agent in the powder slurry in the step (1) is (70-200): 1;
the mass fraction of the dispersant water solution in the step (1) is 5-30%.
6. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the polyolefin resin in the step (2) is at least one of high-density polyethylene, low-density polyethylene, homo polypropylene, co-polypropylene, metallocene polyolefin, polyolefin elastomer, ethylene and long-chain olefin copolymer, ethylene and cyclic olefin copolymer, polybutene-1, polytrimethyl-pentene, polytetramethyl-pentene, polyethylene-vinyl alcohol copolymer and polyethylene-vinyl acetate copolymer.
7. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the diameter of the screw of the primary extruder in the step (2) is 35mm, the length-diameter ratio of the screw is 30:1, and a double-cone homodromous screw is selected.
8. The method of preparing a highly filled filler modified polyolefin composite according to claim 1, characterized in that:
the diameter of the screw of the secondary extruder in the step (3) is 35mm, the length-diameter ratio of the screw is (48-54): 1, and a bi-flat reverse screw is selected.
9. A highly filled filler modified polyolefin composite material, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. Use of the highly filled filler modified polyolefin composite material according to claim 9 in the fields of home appliance housings, consumer goods and automotive materials.
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