CN113666662B - Fly ash-based ceramic polyolefin composition, ceramic polyolefin material, and preparation method and application thereof - Google Patents

Fly ash-based ceramic polyolefin composition, ceramic polyolefin material, and preparation method and application thereof Download PDF

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CN113666662B
CN113666662B CN202010409134.4A CN202010409134A CN113666662B CN 113666662 B CN113666662 B CN 113666662B CN 202010409134 A CN202010409134 A CN 202010409134A CN 113666662 B CN113666662 B CN 113666662B
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fly ash
composition
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CN113666662A (en
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李亚飞
孙小杰
巩思宇
任月庆
孙苗苗
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/045—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/90—Electrical properties
    • C04B2111/92—Electrically insulating materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the technical field of wire and cable materials, and discloses a fly ash-based ceramic polyolefin composition, a ceramic polyolefin material, and a preparation method and application thereof. The composition contains matrix resin, fly ash and a coupling agent; the fly ash contains 26.5-30 wt% of alumina, 11-14 wt% of calcium oxide, 40-45 wt% of silicon oxide, 1-8 wt% of ferric oxide and 1-3 wt% of sodium oxide; and 200-400 parts by weight of fly ash relative to 100 parts by weight of the matrix resin. The ceramic polyolefin material can be used for fire-resistant ceramic and has excellent mechanical properties.

Description

Fly ash-based ceramic polyolefin composition, ceramic polyolefin material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of wire and cable materials, in particular to a fly ash-based ceramic polyolefin composition, a ceramic polyolefin material, a preparation method and application thereof.
Background
The ceramic polyolefin material has excellent performance of common polymers at normal temperature, can form a self-supporting ceramic structure at high temperature, can protect the insulated wire core and ensure the normal operation of a line system in case of fire, can generate far-reaching influence on the existing fire-resistant wire and cable industry, and has wide development prospect.
The prior porcelain forming filler has the defect of high price.
CN103509237B discloses a fast ceramization fire-resistant cable material, which is prepared from the following component raw materials in parts by weight: 40-50 parts of ethylene-vinyl acetate copolymer (EVA), 30-40 parts of polyethylene, 20-35 parts of natural rubber, 30-40 parts of styrene butadiene rubber, 4-6 parts of compatilizer, 1-2 parts of zinc oxide, 20-30 parts of argil, 10-15 parts of kaolin, 5-6 parts of medical stone, 6-7 parts of garnet, 1-2 parts of 3-aminopropyltrimethoxysilane, 3-4 parts of rapeseed oil, 1-2 parts of pentaerythritol, 1-2 parts of melamine cyanurate, 1-2 parts of molybdenum trioxide, 4-6 parts of ammonium molybdate, 1-2 parts of copper oxide, 1-2 parts of polytetrafluoroethylene micro powder, 10-12 parts of diisobutyl phthalate (DIBP), 6-8 parts of tributyl acetylcitrate, 2-4 parts of epoxy octyl stearate, 1-2 parts of cross-linking agent TAIC, 1-2 parts of ferrocene and 12-15 parts of modified filler, and the mixture is put into a high-speed mixer to be mixed for 4-5min, and then put into a double-screw extruder to be extruded and granulated, and dried by hot air to obtain the fast ceramic fireproof cable material. However, the cable material is complex, the filler ratio is small, and the ceramic compactness and the strength are insufficient.
CN104558804A discloses a ceramic polyolefin material and a preparation method thereof, wherein the raw material components and the weight parts of the components are respectively: 100 parts of ethylene-alpha-olefin copolymer, 150-300 parts of vitrified powder A (lamellar inorganic powder, needle-shaped inorganic powder and fibrous inorganic powder), 20-100 parts of vitrified powder B (borax, ammonium borate, zinc borate and boron frits, low-melting-point phosphate glass powder, low-melting-point borate glass powder and low-melting-point silicate glass powder), 5-40 parts of lubricant and 0.1-1 part of antioxidant are put into an internal mixer for mixing, and when the mixture is mixed to the temperature of 100-115 ℃, the mixture is discharged and is introduced into a double-screw extruder through a conical feeding hopper for melt extrusion and granulation to obtain the vitrified polyolefin material; the elongation at break of the material is 310-420%, but the tensile strength of the material is 4MPa, and the strength can not meet the requirements of sheath materials.
CN105504464A discloses a preparation method of a ceramic polyolefin fire-resistant cable material, which comprises the following components by weight: 40-100 parts of polyolefin, 1-30 parts of compatilizer, 350-500 parts of vitrified powder, 20-200 parts of fluxing agent, 20-100 parts of flame retardant, 2-20 parts of lubricant and 1-10 parts of antioxidant; firstly, adding polyolefin, compatilizer, flame retardant and antioxidant into an internal mixer in proportion for banburying; then adding the porcelain powder and the lubricant for banburying, and then adding the fluxing agent for banburying uniformly; and adding the mixture into a double screw for extrusion molding to obtain the ceramic polyolefin fire-resistant cable material. The material has good ceramic forming performance, the tensile strength is 9.8MPa, the elongation at break is 160-210%, and the flame retardant grade is V-0. However, the preparation steps are complicated and the ceramic powder, the fluxing agent and the like need to be processed for multiple times.
Particularly, the materials prepared by the prior art do not meet the requirements of simple formula, convenient processing and can not simultaneously meet the requirements of fire resistance, porcelain appearance and excellent mechanical property.
Therefore, the research and development of a material which has both fireproof and porcelain properties and excellent mechanical properties is of great significance.
Disclosure of Invention
The invention aims to overcome the defects that the prepared ceramic polyolefin material in the prior art cannot simultaneously meet the requirements of fire resistance and ceramic property and has excellent mechanical property, and the defects of complex preparation formula and complex processing, and provides a fly ash-based ceramic polyolefin composition, a ceramic polyolefin material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a fly ash-based ceramicized polyolefin composition, wherein the composition comprises a base resin, fly ash and a coupling agent; wherein the fly ash contains aluminum oxide, calcium oxide, silicon oxide, iron oxide and sodium oxide, and based on the total weight of the fly ash, the content of the aluminum oxide is 26.5-30 wt%, the content of the calcium oxide is 11-14 wt%, the content of the silicon oxide is 40-45 wt%, the content of the iron oxide is 1-8 wt%, and the content of the sodium oxide is 1-3 wt%; and 200-400 parts by weight of the fly ash relative to 100 parts by weight of the matrix resin.
In a second aspect, the present invention provides a method for preparing a ceramified polyolefin material from the composition as described above, wherein the method comprises:
(1) Carrying out banburying mixing on matrix resin, fly ash and a coupling agent under the stirring condition to obtain a mixed material;
(2) And carrying out extrusion granulation and drying treatment on the mixed material to obtain the ceramic polyolefin material.
In a third aspect of the invention there is provided a ceramicized polyolefin material prepared by the process as hereinbefore described.
The invention provides a fourth aspect of the invention provides an application of the ceramic polyolefin material in the preparation of electric wires and cables.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) In the technical scheme of the invention, the fly ash subjected to coupling treatment is introduced as a low-melting-point porcelain forming material, so that the porcelain forming method has the advantage of high-efficiency porcelain forming.
(2) The invention can regulate and control the ceramic forming performance and the mechanical property of the ceramic polyolefin material by controlling the composition (the content of alumina, calcium oxide, silicon oxide, iron oxide and sodium oxide) and the particle size of the fly ash.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a fly ash-based ceramic polyolefin composition, wherein the composition contains a matrix resin, fly ash and a coupling agent; wherein the fly ash contains aluminum oxide, calcium oxide, silicon oxide, iron oxide and sodium oxide, and based on the total weight of the fly ash, the content of the aluminum oxide is 26.5-30 wt%, the content of the calcium oxide is 11-14 wt%, the content of the silicon oxide is 40-45 wt%, the content of the iron oxide is 1-8 wt%, and the content of the sodium oxide is 1-3 wt%; and 200-400 parts by weight of fly ash relative to 100 parts by weight of the matrix resin.
The inventor of the invention finds that the existing commonly used porcelain forming filler has the defect of high price, the fly ash is used as a dangerous waste product of a coal-fired power plant, contains aluminum oxide, calcium oxide, silicon oxide, iron oxide and sodium oxide porcelain forming components, and a coupling agent is introduced to carry out coupling treatment on the fly ash to prepare the ceramic polyolefin material.
In the present invention, the fly ash mainly contains alumina, calcium oxide, silicon oxide, iron oxide, and sodium oxide porcelain-forming components, and also contains a small amount of titanium oxide, barium oxide, and the like. Therefore, the total content of alumina, calcium oxide, silica, iron oxide and sodium oxide is less than 100%.
According to the invention, preferably, based on the total weight of the fly ash, the content of the aluminum oxide is 27-29 wt%, the content of the calcium oxide is 11-13 wt%, the content of the silicon oxide is 41-43 wt%, the content of the iron oxide is 1-2 wt%, and the content of the sodium oxide is 1.5-3 wt%.
According to the present invention, it is preferable that the fly ash is 250 to 350 parts by weight with respect to 100 parts by weight of the base resin. In the present invention, the content of the fly ash is limited to the above range, which has the advantages that the material can form a strong and stable porcelain and maintain excellent mechanical properties.
According to the present invention, the content of the alumina is 26.5 to 30% by weight, and specifically, may be any value in the range of 26.5% by weight, 27% by weight, 27.5% by weight, 28% by weight, 28.5% by weight, 29% by weight, 29.5% by weight, 30% by weight, or any two of these values, for example. Similarly, the ranges of the amounts of the components of the ceramic-forming materials, calcium oxide, silicon oxide, iron oxide and sodium oxide, are also intended to mean any value within the range defined by any two of the endpoints of the defined ranges of values.
According to the invention, it is noted that 200 to 400 parts by weight of fly ash, relative to 100 parts by weight of the base resin, refers to any value in the range defined by any two of the two end-point values of the range values.
According to the invention, the fly ash has an average particle size of 2500-5000 meshes, preferably 3500-5000 meshes.
According to the invention, the particle diameter D of the fly ash 50 Satisfies the following conditions: d is not less than 1.5 mu m 50 4 μm or less, more preferably 1.5 μm or less, D 50 3 μm or less, more preferably 1.5 μm or less, D 50 Less than or equal to 2 mu m; in the present invention, D 50 And testing by using a laser particle analyzer.
According to the invention, the particle diameter D of the fly ash 90 Satisfies the following conditions: d is not less than 3 mu m 90 8 μm or less, more preferably 3 μm or less, D 90 5 μm or less, more preferably 3 μm or less, D 90 Less than or equal to 4 mu m; in the present invention, D 90 And testing by using a laser particle analyzer.
In the present invention, the particle size of the fly ash is limited to the range, and the aim is that the fly ash with smaller particle size has lower vitrification temperature, and can improve the toughness of the composite material and reduce the influence on the tensile property of the matrix resin. However, the superfine fly ash needs to be sorted more finely, the cost is higher, and agglomeration is easy to occur in the processing process.
In the invention, the fly ash is from Beijing low-carbon clean energy institute, and the mark is NF0004A.
According to the invention, the coupling agent is selected from one or more of silane coupling agents, titanate coupling agents and aluminate coupling agents; specifically, the coupling agent is selected from one or more of a silane coupling agent A171, a silane coupling agent KH570, a titanate coupling agent 201 and an aluminate coupling agent 101; preferably, the coupling agent is selected from a silane coupling agent KH570.
In the invention, the coupling agent can modify the fly ash, and specifically, the principle is as follows: the coupling agent molecule has active groups which have chemical reaction and physical action with inorganic matters and active groups which have chemical reaction with organic matters, and the dispersibility and the interface compatibility of the coupling agent molecule in matrix resin are improved after surface modification treatment.
According to the present invention, the coupling agent is 0.3 to 1 part by weight with respect to 100 parts by weight of the base resin; more preferably, the coupling agent is 0.5 to 0.8 parts by weight with respect to 100 parts by weight of the base resin. In the present invention, the content of the coupling agent is limited to the aforementioned range, and the surface of the inorganic filler such as fly ash and hydroxide can be sufficiently modified, and the dispersibility and compatibility of the inorganic filler in the matrix resin can be improved.
According to the invention, the linear low density polyethylene has a melt flow rate of 1.0 to 4.0g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91 to 0.93g/cm 3 The melting point is 105-125 ℃; preferably, the linear low density polyethylene has a melt flow rate of 1.8 to 2.2g/10min at 190 ℃ under a load of 2.16kg and a density of 0.915 to 0.925g/cm 3 The melting point is 115-120 ℃. In the present invention, the linear low density polyethylene is selected because it enables the preparation of a ceramicized polyolefin material from the fly ash-based ceramicized polyolefin composition having a high tensile strength and a suitable elongation at break.
According to the invention, the vinyl acetate content of the ethylene-vinyl acetate copolymer is from 12 to 45% by weight, more preferably from 18 to 28% by weight. The ethylene-vinyl acetate copolymer has a melt flow rate of 2.6-2.7g/10min at 190 ℃ under a load of 2.16kg and a density of 0.939-0.940g/cm 3 The melting point is 85-86 ℃.
According to the invention, the weight ratio of the contents of the linear low density polyethylene and the ethylene-vinyl acetate copolymer is (0.2-1): 1, more preferably (0.25-0.4): 1. in the invention, the ethylene-vinyl acetate copolymer has polar groups, is beneficial to the filling material of the inorganic flame retardant, and has higher elongation at break but lower tensile strength; whereas linear low density polyethylene provides higher tensile strength; the weight ratio of the contents of the linear low-density polyethylene and the ethylene-vinyl acetate copolymer is limited to be within the range, so that the ceramic polyolefin material prepared from the fly ash-based ceramic polyolefin composition has higher elongation at break and higher tensile strength.
According to the invention, the composition also contains a compatibilizer, a flame retardant, a fluxing agent and an antioxidant.
According to the invention, the compatibilizer is selected from one or more of acrylic-type compatibilizers, polyethylene grafted maleic anhydride (abbreviated as PE-g-MAH in chemistry), ethylene-vinyl acetate copolymer grafted maleic anhydride and polyolefin elastomer grafted maleic anhydride; preferably, the compatibilizer is selected from polyethylene grafted maleic anhydride and/or ethylene-vinyl acetate copolymer grafted maleic anhydride. In the invention, the compatilizer has the functions of improving the interface compatibility of the inorganic filler and the nonpolar resin, facilitating the transmission of stress on the interface and improving the mechanical property of the material. .
According to the invention, the flame retardant is selected from one or more of aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, ammonium polyphosphate and coated red phosphorus; in the present invention, preferably, the flame retardant is not built, i.e., the flame retardant is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, ammonium polyphosphate, coated red phosphorus; more preferably, the flame retardant is aluminum hydroxide; the aluminum hydroxide is decomposed at a lower temperature to play a role in flame retardance; at higher temperatures, however, under the action of low-melting-point fluxes, fly ash can form firm ceramics, which prevents combustion. Therefore, a flame retardant having an excessively wide flame-retardant temperature is not required. In the present invention, the coated red phosphorus is modified red phosphorus.
According to the invention, the fluxing agent is selected from one or more of zinc borate, low-melting glass powder and glass fiber; preferably, the fluxing agent is zinc borate and/or a low melting point glass frit.
According to the invention, the antioxidant is selected from one or more of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (Irganox 1010), 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (1330), tris [2, 4-di-tert-butylphenyl ] phosphite (Irgafos 168) and distearyl thiodipropionate (DSTP); preferably, the antioxidant is selected from two combinations of Irganox 1010 and Irgafos 168. In the invention, the antioxidant has the functions of delaying or preventing the oxidation process of the matrix resin during processing and storage, improving the thermal stability and prolonging the service life.
According to the invention, relative to 100 parts by weight of the matrix resin, 5-20 parts by weight of the compatilizer, 50-100 parts by weight of the flame retardant, 20-50 parts by weight of the fluxing agent and 0.2-1.0 part by weight of the antioxidant are added; preferably, the compatibilizer is 8 to 15 parts by weight, the flame retardant is 60 to 90 parts by weight, the flux is 25 to 40 parts by weight, and the antioxidant is 0.3 to 0.6 part by weight, relative to 100 parts by weight of the base resin.
According to the invention, the composition also contains a processing aid selected from one or more of PE wax, silicone oil, silicone, stearic acid, zinc stearate and calcium stearate.
According to the present invention, the processing aid is 0.1 to 1.0 part by weight, preferably 0.5 to 0.8 part by weight, relative to 100 parts by weight of the base resin.
In a second aspect, the present invention provides a method for preparing a ceramified polyolefin material from the composition as described above, wherein the method comprises:
(1) Carrying out banburying mixing on matrix resin, fly ash and a coupling agent under the stirring condition to obtain a mixed material;
(2) And carrying out extrusion granulation and drying treatment on the mixed material to obtain the ceramic polyolefin material.
According to the invention, in step (1), the conditions of the banburying mixing comprise: stirring at 30-60rpm at 125-145 deg.C for 8-18min; preferably, the stirring speed is 40-50rpm, the temperature is 130-140 ℃, and the time is 10-13min. In the invention, too high stirring speed or too high temperature can cause the viscosity of the mixed material to be low, thus being not beneficial to shearing and dispersing; too slow stirring speed or too low temperature, longer mixing time, influence efficiency.
According to the invention, in step (2), the extrusion granulation conditions comprise: the rotating speed is 80-180rpm, and the temperature is 125-145 ℃; preferably, the speed of rotation is 90-170rpm and the temperature is 130-140 ℃.
According to the invention, in step (2), the mixing is carried out in a cone double forced-feed single-screw extruder. In the invention, the single screw extruder with conical double forced feeding is defined because the mixed material after banburying can be continuously and stably fed into the single screw extruder for granulation, the friction is small, and the dispersion effect is good. Wherein the length-diameter ratio of the screw of the single-screw extruder is 16/1-40/1, preferably 18/1, the rotating speed of the screw is 80-180rpm, preferably 100rpm, and the temperature of the screw extrusion blending is 130-140 ℃, preferably 135 ℃.
According to the invention, preferably, the raw materials (matrix resin, fly ash, fluxing agent, flame retardant, compatilizer, coupling agent and antioxidant) are weighed according to the proportion and put into an internal mixer for mixing to obtain an internal mixing mixed material; and (3) putting the banburying mixed material into a single-screw extruder with conical double forced feeding, granulating by using underwater cutting after extrusion, drying in a hot air dryer after vibration dehydration, and thus obtaining the ceramic polyolefin material.
According to the invention, more preferably, the raw materials (matrix resin, fly ash, fluxing agent, flame retardant, compatilizer, coupling agent, antioxidant and processing aid) are weighed according to the proportion and put into an internal mixer for mixing to obtain an internal mixing mixed material; and (3) putting the banburying mixture into a single-screw extruder with conical double forced feeding, granulating by using underwater cutting after extrusion, vibrating and dehydrating, and then drying in a hot air dryer to obtain the ceramic polyolefin material.
According to the invention, the ceramic polyolefin material is added into a forming die, and the die pressing and forming are carried out under certain conditions, so as to obtain a corresponding sample.
In the present invention, the banburying-single screw extrusion granulator set is available from Kunshan Kexin rubber and plastic machinery Co., ltd, and has a model number of KS-52/100.
In a third aspect, the present invention provides a ceramicized polyolefin material prepared by the method as hereinbefore described.
According to the invention, the ceramic polyolefin material has tensile strength of more than 9MPa, elongation at break of more than or equal to 150 percent and volume resistivity of 1 multiplied by 10 13 To 1X 10 14 Omega cm, the oxygen index is more than or equal to 26; preferably 9.3-10.8MPa, elongation at break 150-210%, and volume resistivity of 6X 10 13 To 1 × 10 14 Omega cm, oxygen index of 26-32.
In the invention, the temperature is raised to 900 ℃ at a speed of 15 ℃/min, and the porcelain is molded by holding the temperature for 30min under the non-pressure condition, so that the porcelain with good compactness can be obtained.
The invention provides the application of the ceramic polyolefin material in preparing electric wires and cables.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) Tensile strength and elongation at break test method
Weighing weighed composition granules, tabletting by using a 200mm multiplied by 2mm die, cutting a dumbbell-shaped sample according to the GB/T1040.2-2006 requirement, placing the dumbbell-shaped sample in a test room for 24 hours, testing by using an Instron5965 type testing machine according to the GB/T1040.2-2006 method, wherein the tensile rate is 200mm/min, and taking the maximum tensile stress borne by the sample at the time of fracture as the tensile strength and the strain change value as the elongation at break of the composition material.
(2) Volume resistivity test method
Each sample was tested in parallel 3 times according to the GB/T1410-2006 test, and the average was taken.
(3) Limit oxygen index test method
The weighed composition pellets were molded into 80mm by 10mm by 4mm bars, the thickness of the samples being 4.0mm, according to GB/T2406.2-2009 test.
(4) Method for testing performance of ceramic product
And (3) putting the crucible for containing the sample into a muffle furnace, heating from room temperature to 900 ℃ at a speed of 15 ℃/min in an air atmosphere, and preserving heat for 30min. And observing the shape of the sintered sample, and judging whether the sample is compact and complete.
(5) In the examples and comparative examples:
the linear low density polyethylene is purchased from Shenhua coal oil Baotou company, and the mark is DFDA7042; the selected EVA was purchased from China petrochemical Beijing Yanshan division, and the brand number is 18J3; the mass ratio of the two is 1;
the flame retardant is aluminum hydroxide with the brand number OL-100;
the grade of the fly ash is NF0004A;
the fluxing agent is low-melting point glass powder with the brand number D250;
the selected compatilizer is ethylene-vinyl acetate copolymer grafted maleic anhydride, and the grade is OREVAC9318;
the selected coupling agent is a silane coupling agent KH-570;
the selected processing aids are PE wax and zinc stearate, and the mass ratio is 2;
the selected antioxidants are Irganox 1010 and Irgafos 168, and the mass ratio is 1:1.
example 1
This example illustrates a ceramicized polyolefin material prepared using the fly ash-based ceramicized polyolefin composition of the present invention.
(1) 2000g of fly ash (average particle size 5000 mesh, D) 50 1.5-2.0 μm, D 90 3.0-4.0 mu m, based on the total weight of the fly ash, the content of the aluminum oxide is 28 wt%, the content of the calcium oxide is 12 wt%, the content of the silicon oxide is 42 wt%, the content of the iron oxide is 1.5 wt%, and the content of the sodium oxide is 2 wt%), and 50g of the coupling agent KH-570 are mixed, heated to 115 ℃, stirred at a constant temperature for 15min, and then mixed with 750g of an ethylene-vinyl acetate copolymer (EVA, the brand is 18J3, the content of the vinyl acetate is 18 wt%, the melt flow rate at 190 ℃ under a load of 2.16kg is 2.6g/10min, and the density is 0.939g/cm 3 Melting point 86 ℃ C.), 250g of a linear low density polyethylene (DFDA 7042 having a melt flow rate of 2g/10min at 190 ℃ under a 2.16kg load, and a density of 0.92g/cm 3 Melting point 119 ℃), 800g of aluminium hydroxide, 200g of low-melting glass powder (D250), 100g of ethylene-vinyl acetate copolymer grafted maleic anhydride (trade name OREVAC 9318), 50g of processing aids (PE wax and zinc stearate in a mass ratio of 2: 1) Adding the mixture into an internal mixer, mixing for 12min till the mixture is uniform, and then putting the mixture into a single-screw extruder with cone double forced feeding for melt blending and underwater pelletizing to prepare the ceramic polyolefin material. Wherein the length-diameter ratio of the screw of the single-screw extruder is 18/1, the rotating speed of the screw is 100rpm, and the extrusion and blending temperature of the screw is 18/1The temperature was 135 ℃.
Example 2
This example is illustrative of a ceramicized polyolefin material prepared with the fly ash-based ceramicized polyolefin composition of the present invention.
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: based on the total weight of the fly ash, the content of the aluminum oxide is 27 wt%, the content of the calcium oxide is 11 wt%, the content of the silicon oxide is 41 wt%, the content of the iron oxide is 1 wt%, and the content of the sodium oxide is 1.5 wt%; and the individual components and the contents of the components are shown in table 1.
Example 3
This example is illustrative of a ceramicized polyolefin material prepared with the fly ash-based ceramicized polyolefin composition of the present invention.
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: based on the total weight of the fly ash, the content of the aluminum oxide is 29 wt%, the content of the calcium oxide is 13 wt%, the content of the silicon oxide is 43 wt%, the content of the iron oxide is 2 wt%, and the content of the sodium oxide is 3 wt%; and the individual components and the contents of the components are shown in table 1.
Example 4
This example illustrates a ceramicized polyolefin material prepared using the fly ash-based ceramicized polyolefin composition of the present invention.
A ceramicized polyolefin material was prepared under the same conditions as in example 1 except that: based on the total weight of the fly ash, the content of aluminum oxide is 26.5 wt%, the content of calcium oxide is 11 wt%, the content of silicon oxide is 40 wt%, the content of iron oxide is 1 wt%, and the content of sodium oxide is 1 wt%; and the individual components and the contents of the components are shown in table 1.
Example 5
This example illustrates a ceramicized polyolefin material prepared using the fly ash-based ceramicized polyolefin composition of the present invention.
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: based on the total weight of the fly ash, the content of alumina is 30 wt%, the content of calcium oxide is 14 wt%, the content of silicon oxide is 45 wt%, the content of ferric oxide is 8 wt%, and the content of sodium oxide is 3 wt%; and the components and the contents of the components are shown in table 1.
Example 6
This example illustrates a ceramicized polyolefin material prepared using the fly ash-based ceramicized polyolefin composition of the present invention.
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: the individual components and the contents of the components are shown in table 1.
Comparative examples 1 to 3
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: the individual components and the amounts of the components are shown in table 3.
Comparative example 4
A ceramicized polyolefin material was prepared according to the same conditions as in example 1 except that: the components and the content of the components are shown in table 3, wherein the low-alumina fly ash contains the following components: based on the total weight of the low-alumina fly ash, the content of the alumina is 20 wt%, the content of the calcium oxide is 18 wt%, the content of the silica is 40 wt%, the content of the iron oxide is 1.5 wt%, and the content of the sodium oxide is 2 wt%.
Test example 1
200g of the ceramicized polyolefin materials prepared in examples 1 to 6 and comparative examples 1 to 4 were weighed, molded into a sample of 200 mm. Times.200 mm. Times.2 mm, cut into tensile specimens, and tested for corresponding mechanical properties, the test results of examples 1 to 6 are shown in Table 2, and the test results of comparative examples 1 to 4 are shown in Table 4.
Test example 2
200g of the ceramicized polyolefin materials prepared in examples 1 to 6 and comparative examples 1 to 4 were weighed and molded into 80 mm. Times.10 mm. Times.4 mm specimens, and the limiting oxygen index was measured, and the results of the tests for examples 1 to 6 are shown in Table 2 and the results of the tests for comparative examples 1 to 4 are shown in Table 4.
Test example 3
The ceramicized polyolefin materials prepared in examples 1-6 and comparative examples 1-4 were characterized by volume resistivity and porcelain forming property, and the test results of examples 1-6 are shown in Table 2 and the test results of comparative examples 1-4 are shown in Table 4.
TABLE 1
Figure BDA0002492483970000141
TABLE 2
Figure BDA0002492483970000151
TABLE 3
Figure BDA0002492483970000152
TABLE 4
Figure BDA0002492483970000153
The results in tables 1 and 4 show that the ceramic polyolefin materials prepared by the fly ash-based ceramic polyolefin composition in examples 1 to 6 of the present invention have excellent mechanical properties, good flame retardancy, good ceramic formation property, and significantly better effect.
In comparative examples 1 to 4, the effect was poor because of poor mechanical properties and poor porcelain forming properties of comparative examples 1 and 4.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (27)

1. A fly ash-based ceramized polyolefin composition, which is characterized by comprising a matrix resin, fly ash and a coupling agent; the fly ash contains 26.5-30 wt% of alumina, 11-14 wt% of calcium oxide, 40-45 wt% of silicon oxide, 1-8 wt% of iron oxide and 1-3 wt% of sodium oxide, based on the total weight of the fly ash; and 200-400 parts by weight of the fly ash per 100 parts by weight of the base resin; the coupling agent is 0.3 to 1 part by weight with respect to 100 parts by weight of the base resin.
2. The composition as claimed in claim 1, wherein the content of the alumina is 27-29 wt%, the content of the calcium oxide is 11-13 wt%, the content of the silica is 41-43 wt%, the content of the iron oxide is 1-2 wt%, and the content of the sodium oxide is 1.5-3 wt%, based on the total weight of the fly ash; and the fly ash is 250-350 parts by weight relative to 100 parts by weight of the matrix resin.
3. The composition of claim 1, wherein,
the average grain diameter of the fly ash is 2500-5000 meshes.
4. The composition according to claim 3, wherein,
the particle diameter D of the fly ash 50 Satisfies the following conditions: d is less than or equal to 1.5 mu m 50 ≤4μm。
5. The composition of claim 3, wherein,
the particle diameter D of the fly ash 90 Satisfies the following conditions: d is not less than 3 mu m 90 ≤8μm。
6. The composition as claimed in claim 1, wherein the coupling agent is selected from one or more of silane-based coupling agents, titanate-based coupling agents and aluminate-based coupling agents.
7. The composition of claim 1, wherein,
the coupling agent is 0.5 to 0.8 parts by weight with respect to 100 parts by weight of the base resin.
8. The composition of any of claims 1-7, wherein the matrix resin comprises linear low density polyethylene and/or ethylene vinyl acetate copolymer.
9. The composition according to claim 8, wherein,
the linear low density polyethylene has a melt flow rate of 1-4g/10min at 190 ℃ under a load of 2.16kg and a density of 0.91-0.93g/cm 3 The melting point is 105-125 ℃.
10. The composition of claim 8, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 12-45% by weight.
11. The composition according to claim 10, wherein,
the ethylene-vinyl acetate copolymer has a vinyl acetate content of 18 to 28 wt%.
12. The composition according to claim 8, wherein,
the weight ratio of the linear low-density polyethylene to the ethylene-vinyl acetate copolymer is (0.2-1): 1.
13. the composition of claim 12, wherein,
the weight ratio of the linear low density polyethylene to the ethylene-vinyl acetate copolymer is (0.25-0.4): 1.
14. the composition of any one of claims 1-7, wherein the composition further comprises a compatibilizing agent, a flame retardant, a fluxing agent, and an antioxidant.
15. The composition of claim 14, wherein the compatibilizer is selected from one or more of an acrylic-type compatibilizer, polyethylene grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride, and polyolefin elastomer grafted maleic anhydride.
16. The composition of claim 14, wherein,
the flame retardant is selected from one or more of aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, ammonium polyphosphate and coated red phosphorus.
17. The composition of claim 14, wherein,
the fluxing agent is selected from one or more of zinc borate, low-melting-point glass powder and glass fiber.
18. The composition of claim 14, wherein,
the antioxidant is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris [2, 4-di-tert-butylphenyl ] phosphite and distearyl thiodipropionate.
19. The composition as set forth in claim 14, wherein the compatibilizer is 5 to 20 parts by weight, the flame retardant is 50 to 100 parts by weight, the flux is 20 to 50 parts by weight, and the antioxidant is 0.2 to 1 part by weight, relative to 100 parts by weight of the base resin.
20. A process for preparing a ceramicized polyolefin material from the composition according to any one of claims 1 to 13, the process comprising:
(1) Carrying out banburying mixing on matrix resin, fly ash and a coupling agent under the stirring condition to obtain a mixed material;
(2) And extruding, granulating and drying the mixed material to obtain the ceramic polyolefin material.
21. The method of claim 20, wherein in step (1), the conditions of said banburying mixing comprise: stirring speed of 30-60rpm at 125-145 deg.C for 8-18min.
22. The method of claim 20, wherein,
in step (2), the extrusion granulation conditions include: the rotation speed is 80-180rpm, and the temperature is 125-145 ℃.
23. A process for preparing a ceramified polyolefin material from the composition according to any one of claims 14 to 19, the process comprising:
(1) Carrying out banburying mixing on matrix resin, fly ash, a coupling agent, a compatilizer, a flame retardant, a fluxing agent and an antioxidant under the stirring condition to obtain a mixed material;
(2) And carrying out extrusion granulation and drying treatment on the mixed material to obtain the ceramic polyolefin material.
24. A ceramicized polyolefin material prepared according to the method of any one of claims 20 to 23.
25. The ceramified polyolefin material according to claim 24, wherein the ceramified polyolefin material has a tensile strength of > 9MPa, an elongation at break of 150% or more, and a volume resistivity of 1 x 10 13 To 1X 10 14 Omega cm, oxygen index is more than or equal to 26.
26. The ceramified polyolefin material according to claim 25, wherein,
the ceramic polyolefin material has tensile strength of 9.3-10.8MPa, elongation at break of 150-210% and volume resistivity of 6 x 10 13 To 1X 10 14 Omega cm, and oxygen index of 26-32.
27. Use of a ceramicized polyolefin material according to any one of claims 24 to 26 for the preparation of electric wire and cable.
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