CN113388208A - Desulfurized fly ash modified polypropylene composite material and preparation method thereof - Google Patents
Desulfurized fly ash modified polypropylene composite material and preparation method thereof Download PDFInfo
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- CN113388208A CN113388208A CN202110880653.3A CN202110880653A CN113388208A CN 113388208 A CN113388208 A CN 113388208A CN 202110880653 A CN202110880653 A CN 202110880653A CN 113388208 A CN113388208 A CN 113388208A
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- 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
- C08L23/14—Copolymers of propene
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- 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
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- 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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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a desulfurized fly ash modified polypropylene composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 50-88 parts of polypropylene, 10-30 parts of desulfurized fly ash, 2-15 parts of toughening agent, 0.2-0.8 part of coupling agent, 0.2-0.8 part of lubricant, 0.2-0.8 part of antioxidant and 0.2-0.8 part of light stabilizer. The invention utilizes the coupling agent to carry out surface modification on the desulfurized fly ash with good adsorption performance, so as to prepare the polypropylene composite material with excellent mechanical property and low emission, and realize the resource and high-valued application of the desulfurized fly ash. The invention can be widely applied to the field of automobile interior and exterior polypropylene materials, and effectively improves the VOC emission problem of the composite material.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a desulfurized fly ash modified polypropylene composite material and a preparation method thereof.
Background
China is not only the country with the largest global coal reserves and yields, but also the country with the largest global coal consumption. In the fields of thermal power generation, iron and steel smelting and the like, a great amount of coal is consumed every year, and a great amount of air pollutants, particularly SO, are generated2. In order to control and reduce SO2And (4) discharging amount and entering a high-speed development stage of a sintering flue gas desulfurization project. The application of the semi-dry and dry desulfurization process effectively reduces SO2The amount of discharged, but also a large amount of desulfurized fly ash is produced. At present, the development and application of the desulfurization ash in China are still in the development and exploration stage, and a large amount of desulfurization ash is stacked and treated, so that secondary pollution is easily caused.
When the desulfurized ash is generated under the high-temperature condition, gas-solid reaction occurs, the desulfurized product is difficult to generate liquid phase, and the desulfurized ash can generate obvious solid phase diffusion effect but cannot be densified, so that the desulfurized ash has small particle size, loose and porous surface structure and better adsorption capacity. The main composition of the desulfurized fly ash is CaSO3、CaCO3、Ca(OH)2、CaCO3、SiO2And the like.
In recent years, the economy of China is rapidly developed, the income of residents is greatly improved, so that the consumption and the upgrade of the residents are accelerated, and automobiles are used as walking tools to go into thousands of households. Although the modified polypropylene plays a positive role in the light weight and functional development of automobiles, when the modified polypropylene is used as an automobile interior trim part, Volatile Organic Compounds (VOC) such as pentacene trialdehyde and the like are generated, so that the environment in the automobile is degraded, and the health of a human body is damaged. At present, the VOC problem of modified plastics is solved by the technologies of adsorbent adsorption, melt devolatilization and the like which are commonly used in the industry. The desulfurized fly ash has smaller particle size and good adsorption performance, so that the desulfurized fly ash modified polypropylene material can be used for obtaining a composite material with excellent mechanical property and low emission, and an effective way is found for resource and high-value application of the desulfurized fly ash.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a desulfurized fly ash modified polypropylene composite material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the desulfurized fly ash modified polypropylene composite material comprises the following components:
50-88 parts of polypropylene, 10-30 parts of desulfurized fly ash, 2-15 parts of toughening agent, 0.2-0.8 part of coupling agent, 0.2-0.8 part of lubricant, 0.2-0.8 part of antioxidant and 0.2-0.8 part of light stabilizer.
The preparation method of the desulfurized fly ash modified polypropylene composite material comprises the following steps:
s1, adding the desulfurized ash into a high-speed mixer, and mixing for 5-10min at the temperature of 80-110 ℃ at 1500 r/min; adding coupling agent, and continuously high-mixing for 5-10 min; discharging the desulfurized ash treated by the coupling agent, and cooling the desulfurized ash to room temperature for later use;
s2, adding the desulfurized ash after being treated by the coupling agent, the polypropylene, the toughening agent, the lubricant, the antioxidant and the light stabilizer into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding into a double-screw extruder through a main feeding port to prepare the modified polypropylene composite material.
Further, the polypropylene is one or two of polypropylene copolymer and polypropylene homopolymer.
Furthermore, the mesh number of the desulfurization ash is 1000-5000 meshes.
Further, the toughening agent is one or more of propylene-alpha olefin copolymer, ethylene-propylene copolymer and ethylene-octene copolymer.
Further, the coupling agent is one or more of a rare earth coupling agent, a titanate coupling agent, an aluminate coupling agent and a silane coupling agent.
Further, the lubricant is one or more of calcium stearate, zinc stearate, ethylene bis stearamide and pentaerythritol stearate.
Further, the oxygen agent is one or more of an antioxidant 1076, an antioxidant 1010, an antioxidant 626 and an antioxidant 168.
Further, the light stabilizer is a hindered amine light stabilizer.
Further, the length-diameter ratio of the double-screw extruder is 48:1, and from the first zone to the twelfth zone, the temperature of the screw cylinder of the extruder is 80 +/-10 ℃, 100 +/-10 ℃, 130 +/-10 ℃, 180 +/-10 ℃, 190 +/-10 ℃, 200 +/-10 ℃, 210 +/-10 ℃, 200 +/-10 ℃, the rotation speed of the screw is 400-800r/min, and the vacuum degree is-0.1-0.05 Mpa in sequence.
The invention has the beneficial effects that:
1. the invention provides an effective way for the resource and high-value application of the desulfurized fly ash;
2. the invention utilizes the good adsorption property of the desulfurized fly ash to prepare the polypropylene composite material with excellent mechanical property and low emission.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example 1:
weighing 98 parts by weight of polypropylene copolymer (polypropylene), 2 parts by weight of ethylene-propylene copolymer (toughening agent), 0.2 part by weight of ethylene bis stearamide (lubricant), 0.3 part by weight of antioxidant 1076 (antioxidant) and 0.3 part by weight of light stabilizer UV3808 (good weather resistance, produced by Cyanote corporation in America), adding into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding into a double-screw extruder through a main feeding port for extrusion granulation; the temperature of the screw cylinder of the double-screw extruder from the first zone to the twelfth zone is 75 ℃, 90 ℃, 120 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, 210 ℃, 200 ℃, 200 ℃, the rotating speed of the screw is 500r/min, and the vacuum degree is-0.08 MPa in sequence.
Example 1:
weighing 10 parts of desulfurized ash by weight, adding into a high-speed mixer, and mixing for 7min at the temperature of 100 ℃ at the speed of 1000 r/min; then 0.3 part of rare earth coupling agent is added (the coupling agent used in the embodiment is preferably the series products of Hangzhou Jeccard chemical company Limited), and the high mixing is continued for 5 min; discharging the desulfurized ash treated by the coupling agent, and cooling the desulfurized ash to room temperature for later use;
adding the desulfurized ash after coupling treatment, 83 parts of polypropylene copolymer (polypropylene), 7 parts of propylene-alpha olefin copolymer (toughening agent), 0.3 part of zinc stearate (lubricating agent), 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168 (antioxidant) and 0.5 part of light stabilizer UV-V680 (produced by Cyanote corporation, with good weather resistance) into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding the mixture into a double-screw extruder through a main feeding port for extrusion granulation; the temperature of the screw cylinder of the double-screw extruder from the first zone to the twelfth zone is 80 ℃, 95 ℃, 120 ℃, 190 ℃, 190 ℃, 210 ℃, 220 ℃, 220 ℃, 200 ℃, 190 ℃, the rotating speed of the screw is 700r/min and the vacuum degree is-0.07 Mpa in sequence.
Example 2:
weighing 20 parts of desulfurized ash by weight, adding into a high-speed mixer, and mixing at the temperature of 105 ℃ at 1200r/min for 10 min; then adding 0.6 part of aluminate coupling agent, and continuously high-mixing for 8 min; discharging the desulfurized ash treated by the coupling agent, and cooling the desulfurized ash to room temperature for later use;
adding the desulfurization ash subjected to coupling treatment, 50 parts of co-polypropylene, 20 parts of homo-polypropylene (polypropylene), 10 parts of ethylene-octene copolymer (toughening agent), 0.4 part of pentaerythritol stearate (lubricant), 0.2 part of antioxidant 1010, 0.2 part of antioxidant 626 (antioxidant) and 0.4 part of light stabilizer UV-3808 into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding into a double-screw extruder through a main feeding port for extrusion granulation; the temperature of the screw cylinder of the double-screw extruder from the first zone to the twelfth zone is 80 ℃, 100 ℃, 130 ℃, 190 ℃, 190 ℃, 200 ℃, 210 ℃, 210 ℃, 220 ℃, 220 ℃, 200 ℃, the rotating speed of the screw is 600r/min, and the vacuum degree is-0.08 MPa in sequence.
Example 3:
weighing 25 parts of desulfurized ash by weight, adding into a high-speed mixer, and mixing at the temperature of 90 ℃ at 1500r/min for 10 min; then adding 0.8 part of silane coupling agent, and continuously high-mixing for 10 min; discharging the desulfurized ash treated by the coupling agent, and cooling the desulfurized ash to room temperature for later use;
adding the desulfurization ash subjected to coupling treatment, 30 parts of co-polypropylene, 30 parts of homo-polypropylene (polypropylene), 15 parts of propylene-alpha olefin copolymer (toughening agent), 0.5 part of zinc stearate (lubricant), 0.3 part of antioxidant 1076, 0.3 part of antioxidant 168 (antioxidant) and 0.7 part of light stabilizer UV-3808 into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding into a double-screw extruder through a main feeding port for extrusion granulation; the temperature of the screw cylinder of the double-screw extruder from the first zone to the twelfth zone is 80 ℃, 110 ℃, 130 ℃, 180 ℃, 190 ℃, 210 ℃, 220 ℃, 220 ℃, 210 ℃, 200 ℃, the rotating speed of the screw is 700r/min, and the vacuum degree is-0.07 Mpa in sequence.
The compositions of the starting materials prepared in comparative example 1 and examples 1-3 are shown in table 1 below:
TABLE 1
For the polypropylene composite materials prepared in comparative example 1 and examples 1 to 3, mechanical property test and scratch property were performed according to the relevant test standards, and the test results are shown in table 2 below.
TABLE 2
As can be seen from the test results of the comparative example 1 and the examples 1 to 3, the increase of the addition amount of the desulfurized fly ash is beneficial to the reduction of the atomization content and the improvement of the odor grade of the polypropylene composite material, and the prepared desulfurized fly ash modified polypropylene composite material has excellent mechanical properties. The surface treatment of the desulfurized fly ash by the coupling agent can improve the interface compatibility of the inorganic material and the polypropylene resin and improve the dispersion effect of the desulfurized fly ash, thereby increasing the mechanical property of the polypropylene composite material. The adsorption capacity of the desulfurized ash can effectively absorb the pentaphenyltrialdehyde substance in the polypropylene composite material, thereby reducing the atomization content and the odor grade of the composite material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (10)
1. The desulfurized fly ash modified polypropylene composite material is characterized by comprising the following components:
50-88 parts of polypropylene, 10-30 parts of desulfurized fly ash, 2-15 parts of toughening agent, 0.2-0.8 part of coupling agent, 0.2-0.8 part of lubricant, 0.2-0.8 part of antioxidant and 0.2-0.8 part of light stabilizer.
2. The preparation method of the desulfurized fly ash modified polypropylene composite material based on claim 1, characterized by comprising the following steps:
s1, adding the desulfurized ash into a high-speed mixer, and mixing for 5-10min at the temperature of 80-110 ℃ at 1500 r/min; adding coupling agent, and continuously high-mixing for 5-10 min; discharging the desulfurized ash treated by the coupling agent, and cooling the desulfurized ash to room temperature for later use;
s2, adding the desulfurized ash after being treated by the coupling agent, the polypropylene, the toughening agent, the lubricant, the antioxidant and the light stabilizer into a high-speed mixer, mixing at the normal temperature of 1000r/min for 5min, and finally adding into a double-screw extruder through a main feeding port to prepare the modified polypropylene composite material.
3. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein the polypropylene is one or both of a copolymer polypropylene and a homopolymer polypropylene.
4. The method as claimed in claim 2, wherein the mesh number of the desulfurized fly ash is 1000-5000 mesh.
5. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein the toughening agent is one or more of propylene-alpha olefin copolymer, ethylene-propylene copolymer and ethylene-octene copolymer.
6. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein the coupling agent is one or more of a rare earth coupling agent, a titanate coupling agent, an aluminate coupling agent and a silane coupling agent.
7. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein said lubricant is one or more of calcium stearate, zinc stearate, ethylene bis-stearamide, pentaerythritol stearate.
8. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein the antioxidant is one or more of antioxidant 1076, antioxidant 1010, antioxidant 626 and antioxidant 168.
9. The method for preparing the desulfurized fly ash modified polypropylene composite material according to claim 2, wherein the light stabilizer is a hindered amine light stabilizer.
10. The method as claimed in claim 2, wherein the length-diameter ratio of the twin-screw extruder is 48:1, and the barrel temperature of the extruder from the first zone to the twelfth zone is 80 ± 10 ℃, 100 ± 10 ℃, 130 ± 10 ℃, 180 ± 10 ℃, 190 ± 10 ℃, 200 ± 10 ℃, 200 ± 10 ℃, 210 ± 10 ℃, 210 ± 10 ℃, 210 ± 10 ℃, 200 ± 10 ℃, 200 ± 10 ℃, the screw rotation speed is 400 + 800r/min, and the vacuum degree is-0.1 to-0.05 Mpa.
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|---|---|---|---|---|
| US5130197A (en) * | 1985-03-25 | 1992-07-14 | Ppg Industries, Inc. | Glass fibers for reinforcing polymers |
| US20020014051A1 (en) * | 2000-04-20 | 2002-02-07 | Fraval Hanafi R. | High strength light-weight fiber ash composite material, method of manufacture thereof, and prefabricated structural building members using the same |
| CN102504383A (en) * | 2011-10-19 | 2012-06-20 | 福建龙净脱硫脱硝工程有限公司 | Substrate layer prepared from dry desulfurized ash, aldehyde-free reinforced board and preparation methods |
| CN103589073A (en) * | 2013-10-24 | 2014-02-19 | 合肥会通新材料有限公司 | UV-resistant polypropylene composite material and preparation method thereof |
| CN103589072A (en) * | 2013-10-24 | 2014-02-19 | 合肥会通新材料有限公司 | Low-VOC (Volatile Organic Compound) polypropylene composite material for automotive interior parts and preparation method thereof |
| CN106188832A (en) * | 2016-07-07 | 2016-12-07 | 安徽国风木塑科技有限公司 | A kind of insulation wood-plastic board and preparation method thereof |
| CN109762257A (en) * | 2018-12-17 | 2019-05-17 | 会通新材料股份有限公司 | A kind of automobile-used polypropylene material of low VOC and preparation method thereof |
-
2021
- 2021-08-02 CN CN202110880653.3A patent/CN113388208A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5130197A (en) * | 1985-03-25 | 1992-07-14 | Ppg Industries, Inc. | Glass fibers for reinforcing polymers |
| US20020014051A1 (en) * | 2000-04-20 | 2002-02-07 | Fraval Hanafi R. | High strength light-weight fiber ash composite material, method of manufacture thereof, and prefabricated structural building members using the same |
| CN102504383A (en) * | 2011-10-19 | 2012-06-20 | 福建龙净脱硫脱硝工程有限公司 | Substrate layer prepared from dry desulfurized ash, aldehyde-free reinforced board and preparation methods |
| CN103589073A (en) * | 2013-10-24 | 2014-02-19 | 合肥会通新材料有限公司 | UV-resistant polypropylene composite material and preparation method thereof |
| CN103589072A (en) * | 2013-10-24 | 2014-02-19 | 合肥会通新材料有限公司 | Low-VOC (Volatile Organic Compound) polypropylene composite material for automotive interior parts and preparation method thereof |
| CN106188832A (en) * | 2016-07-07 | 2016-12-07 | 安徽国风木塑科技有限公司 | A kind of insulation wood-plastic board and preparation method thereof |
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