CN102050984A - Method for preparing flame-resistant polymer composite material by utilizing waste red mud - Google Patents
Method for preparing flame-resistant polymer composite material by utilizing waste red mud Download PDFInfo
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- CN102050984A CN102050984A CN201010587825XA CN201010587825A CN102050984A CN 102050984 A CN102050984 A CN 102050984A CN 201010587825X A CN201010587825X A CN 201010587825XA CN 201010587825 A CN201010587825 A CN 201010587825A CN 102050984 A CN102050984 A CN 102050984A
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- red mud
- flame
- red
- percent
- composite material
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Classifications
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- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for preparing a flame-resistant polymer composite material by utilizing waste red mud, belonging to the technical field of the preparation process of inorganic and organic flame-resistant composite materials. The flame-resistant composite material, which is prepared by adopting the waste red mud and the polymer, comprises the following components in percentage by weight: 30-40 percent of polymer, 20-35 percent of red mud, 20-25 percent of nano inorganic flame retardant, 10-13 percent of red phosphorus and 1-3 percent of lubricant. The preparation method comprises the following steps of: firstly, grinding and crushing the red mud in a ball mill; drying and uniformly mixing together with the raw material components in a high-speed mixer; and then, melting, mixing and pelleting with a screw extruder to prepare the flame-resistant polymer composite material. The product of the invention has favorable mechanical properties of materials, excellent flame-resistant effect and low cost and realizes the reutilization of industrial waste red mud.
Description
Technical field
The present invention relates to a kind of method of utilizing the waste residue red mud to prepare ignition resistant polymeric composite, belong to inorganic organic fire-resisting composite material preparation process technical field.
Background technology
Red mud is the waste residue that aluminum oxide produces in process of production, takes on a red color because of containing a large amount of ferric oxide, so be called as red mud.The main ingredient of red mud is SiO
2, CaO, Fe
2O
3, Al
2O
3, Na
2O, K
2O, TiO
2Deng, contain burn alkali composition and other non-ferrous metal of trace in addition.Different because of ore grade, production method and state of the art, composition alters a great deal in the red mud.
At present, the harm that brings to environment of people's growing interest red mud piling up.1 ton of aluminum oxide of about every production will discharge 1.0 ~ 1.8 tons red mud.According to estimates, the aluminum oxide industry annual red mud that produces in the whole world surpasses 6 * 10
7Ton, China's red mud annual emissions reached 4,000 ten thousand tons in 2007, and accumulative total red mud accumulating amount has reached several hundred million tons, all stores up in the open.The stacking of red mud not only takies a large amount of soils, expends more stockyard construction and maintenance cost, and is present in alkali in the red mud to underground infiltration, causes body of groundwater and soil pollution.The dust that exposed red mud forms flies upward with the wind, and atmosphere pollution causes negative impact to human and vegeto-animal existence, worsens ecotope.Along with the red mud quantum of output increase day by day and people to the improving constantly of environmental protection consciousness, limit the harm of red mud to greatest extent, multi-channelly utilize and improve red mud, extremely urgent.
In plastics industry, red mud is mainly as the plastic functional filler.Red mud is done the research of plastic filler and is carried out for many years, and along with the updating of plastic working and surface treatment agent, the application of red mud in plastic industry obtained new progress in recent years.Because the distinctive chemical constitution of red mud makes it have good ageing resistance, thermal stability and flame retardant properties.The open production method of patent CN1461769A with a kind of color plastic profile.Utilize red mud and K2020N one package stabilizer and polyvinyl chloride to mix, produce coffee-like PVC section bar.Its product colourity is full, be smooth to the touch, and cost is 2 times of the common PVC section bar.Be applicable to water service pipe, water shoot, plastic door-window, sheet material and the profiled material of producing PVC series, have good social, economic benefit.Patent CN1068836A discloses the composition that a kind of waste or used plastics utilizes again.Said composition adds a large amount of red muds in waste or used plastics, and adds an amount of thermo-stabilizer and antiaging agent, becomes a kind of new raw material of making architectural shape.Performances such as it is indeformable, wear-resisting, corrosion-resistant, anti-aging that products made thereby has.And utilization of waste material improves environment, and is with low cost.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the waste residue red mud to prepare ignition resistant polymeric composite.
A kind of method of utilizing the waste residue red mud to prepare ignition resistant polymeric composite of the present invention is characterized in that following process and step are arranged:
A, determine composition of raw materials: the raw material of waste residue red mud polymer composites is formed and weight percent:
Polymkeric substance 30～40%,
Red mud 20～35%,
Nanometer inorganic flame retardant 20～25%,
Red phosphorus 10～13%,
Lubricant 1～3%;
Described polymkeric substance is any in polyethylene, polypropylene or the polyvinyl chloride;
Described red mud is an alumina producer Bayer process waste residue red mud;
Described nanometer inorganic flame retardant is any in nano-aluminum hydroxide, magnesium hydroxide, the layered double-hydroxide;
Described red phosphorus is the red phosphorus of chemical pure level;
Described lubricant is any in stearic acid or the paraffin;
B, preparation method
Be 800～1500 orders at grinding in ball grinder to particle diameter at first with red mud, after 80～100 ℃ of following dryings, comprising with above-mentioned other certain proportion raw material that polymkeric substance, inorganic combustion inhibitor, red phosphorus and lubricant join in the high-speed mixer mixes, by screw extrusion press melting mixing, extruding pelletization, obtain granular ignition resistant polymeric composite then; The forcing machine design temperature is 170～190 ℃.
Used red mud is divided into sintering process, Bayer process and integrated process red mud according to the production technique difference of aluminum oxide among the present invention, and China part producer adopts the main component of sintering process and integrated process discharging red mud roughly the same, wherein contains a large amount of 2CaOSiO
2Isoreactivity mineral constituent can directly apply to material of construction production.There is not 2CaOSiO in the Bayer process red mud
2The isoreactivity composition, iron content height in addition, can better play the effect of cooperative flame retardant, and the Bayer process red mud temperature of initial decomposition is 238 ℃, can satisfy the processing temperature requirement of flame-retardant polymer, be subjected to have in the thermal process crystal water to disengage, thereby better flame retardant effect arranged, so the present invention mainly adopts Bayer process red mud than other two kinds of red muds.
Nanometer inorganic flame retardant principal item has aluminium hydroxide, magnesium hydroxide and layered double-hydroxide at present, and this nanometer inorganic flame retardant can not only improve the flame retardant properties of matrix material, also favourable a bit to mechanical property improvement.Red phosphorus can be used as fire retardant and uses separately, is oxidized to noncombustible phosphoric acid liquid film during burning earlier, and then the poly-metaphosphoric acid of dehydration generation, at high temperature makes polymer surfaces form carburization zone, plays fire retardation.In addition, the synergistic fire retardation of red phosphorus and inorganic combustion inhibitor is also fairly obvious, can lower the addition of inorganic combustion inhibitor, thereby improves the processing characteristics and the mechanical property of matrix material.
Innovative point of the present invention and advantage: enlarged the range of application of red mud, met environmental protection and low-carbon economy, prepared the red mud/polymer composites of high added value; By polishing refinement red mud, improve its filling-modified performance; Composite with nanometer inorganic flame retardant, red phosphorus, produced the effect of cooperative flame retardant, not only improve the flame retardant properties of product, and help the mechanical property of product.Adopt the technology of the present invention to prepare the Halogen Recompounded multielement cooperative flame retardant polymer composites based on environmental protection of the requirement that flame retardant effect is good, with low cost, mechanical property can satisfy related products, be applicable to the fire safety evaluating protection of electronic apparatus, material of construction, the important public place of field of traffic.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1:In the present embodiment, the prescription that utilizes the waste residue red mud to prepare the method for ignition resistant polymeric composite is made of the component of following weight percent (wt%):
Polypropylene 30
Red mud 35
Magnesium hydroxide 20
Red phosphorus 13
Lubricant 2
Preparation technology: at first red mud is pulverized in grinding in ball grinder, after particle diameter is 1250 orders, 100 ℃ of following dryings.Composite with each component by recipe ratio, mix in the high-speed mixer, be prepared into product by banburying-single screw extrusion machine extruding pelletization again, wherein the Banbury mixer temperature is 160 ℃, the single screw extrusion machine design temperature is 170～175 ℃.
The limiting oxygen index(LOI) value of products obtained therefrom is 27.5, can be by the vertical combustion V0 level test of UL-94.
Embodiment 2:In the present embodiment, the prescription that utilizes the waste residue red mud to prepare the method for ignition resistant polymeric composite is made of the component of following weight percent (wt%):
Polypropylene 40
Red mud 28
Layered double-hydroxide 20
Red phosphorus 10
Lubricant 2
Preparation technology: at first red mud is pulverized in grinding in ball grinder, after particle diameter is 1250 orders, 80 ℃ of following dryings.Composite with each component by recipe ratio, mix in the high-speed mixer, be prepared into product by the twin screw extruder extruding pelletization again, wherein extruder temperature is set at 170～175 ℃.
The limiting oxygen index(LOI) value of products obtained therefrom is 24.5, can be by the vertical combustion V0 level test of UL-94.
Embodiment 3:In the present embodiment, the prescription that the waste residue red mud prepares the method for ignition resistant polymeric composite is made of the component of following weight percent (wt%):
Polyethylene 35
Red mud 30
Aluminium hydroxide 22
Red phosphorus 11
Lubricant 2
Preparation technology: at first red mud is pulverized in grinding in ball grinder, after particle diameter is 800 orders, 90 ℃ of following dryings.Composite with each component by recipe ratio, mix in the high-speed mixer, be prepared into product by the twin screw extruder extruding pelletization again, wherein extruder temperature is set at 140～150 ℃.
The limiting oxygen index(LOI) value of products obtained therefrom is 28.5, can be by the vertical combustion V0 level test of UL-94.
Embodiment 4:In the present embodiment, the prescription that utilizes the waste residue red mud to prepare the method for ignition resistant polymeric composite is made of the component of following weight percent (wt%):
Polyvinyl chloride 30
Red mud 35
Layered double-hydroxide 22
Red phosphorus 11
Lubricant 2
Preparation technology: at first red mud is pulverized in grinding in ball grinder, after particle diameter is 1250 orders, 90 ℃ of following dryings.Composite with each component by recipe ratio, mix in the high-speed mixer, be prepared into product by the twin screw extruder extruding pelletization again, wherein extruder temperature is set at 180～190 ℃.
Claims (1)
1. method of utilizing the waste residue red mud to prepare ignition resistant polymeric composite is characterized in that following process and step are arranged:
A, determine composition of raw materials: the raw material of waste residue red mud polymer composites is formed and weight percent:
Polymkeric substance 30～40%,
Red mud 20～35%,
Nanometer inorganic flame retardant 20～25%,
Red phosphorus 10～13%,
Lubricant 1～3%;
Described polymkeric substance is any in polyethylene, polypropylene or the polyvinyl chloride;
Described red mud is an alumina producer Bayer process waste residue red mud;
Described nanometer inorganic flame retardant is any in nano-aluminum hydroxide, magnesium hydroxide, the layered double-hydroxide;
Described red phosphorus is the red phosphorus of chemical pure level;
Described lubricant is any in stearic acid or the paraffin;
B, preparation method: be 800～1500 orders at grinding in ball grinder to particle diameter at first with red mud, after 80～100 ℃ of following dryings, comprising with above-mentioned other certain proportion raw material that polymkeric substance, inorganic combustion inhibitor, red phosphorus and lubricant join in the high-speed mixer mixes, by screw extrusion press melting mixing, extruding pelletization, obtain granular ignition resistant polymeric composite then; The forcing machine design temperature is 170～190 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010587825XA CN102050984A (en) | 2010-12-15 | 2010-12-15 | Method for preparing flame-resistant polymer composite material by utilizing waste red mud |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010587825XA CN102050984A (en) | 2010-12-15 | 2010-12-15 | Method for preparing flame-resistant polymer composite material by utilizing waste red mud |
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|---|---|
| CN102050984A true CN102050984A (en) | 2011-05-11 |
Family
ID=43955818
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|---|---|---|---|
| CN201010587825XA Pending CN102050984A (en) | 2010-12-15 | 2010-12-15 | Method for preparing flame-resistant polymer composite material by utilizing waste red mud |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276919A (en) * | 2011-08-08 | 2011-12-14 | 中山市点石塑胶有限公司 | Flame-retardant polypropylene composite material and preparation method thereof |
| CN102746562A (en) * | 2012-07-31 | 2012-10-24 | 王鸿 | Window material, preparing method and application thereof |
| CN102766290A (en) * | 2012-07-31 | 2012-11-07 | 王鸿 | Hot pressed plate and production method and application thereof |
| CN106753440A (en) * | 2016-12-29 | 2017-05-31 | 武汉工程大学 | The black paste produced in vitamin B6 industrial processes is in wood powder carbonization process as the application of fire retardant |
| RU2645511C2 (en) * | 2013-01-22 | 2018-02-21 | ФЛУОРХЕМИ ГмбХ ФРАНКФУРТ | Modified carbonized red sludge |
| CN108219253A (en) * | 2018-01-19 | 2018-06-29 | 广西大学 | A kind of expansion type flame retardant of fire retardant low-density polyethylene |
| CN108484983A (en) * | 2018-04-19 | 2018-09-04 | 安徽工业大学 | A kind of red mud with high efficiency flame retardance-SILICA FUME compounded rubber filler and preparation method thereof |
| CN109161075A (en) * | 2018-07-25 | 2019-01-08 | 山东理工大学 | It is a kind of using biomass fuel clinker as the composite material and preparation method of raw material |
| CN111117148A (en) * | 2020-01-03 | 2020-05-08 | 滨州学院 | Preparation method of red mud composite resin-based friction material |
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| CN1068836A (en) * | 1992-07-17 | 1993-02-10 | 保定市裕南工程处阳台封闭材料厂 | A kind of composition that contains waste or used plastics |
| CN1369515A (en) * | 2001-02-16 | 2002-09-18 | 王林元 | Process for treating colour of red clay-plastic section |
| CN101235174A (en) * | 2008-02-26 | 2008-08-06 | 上海大学 | Environmental protection halogen-free anti-flaming polypropylene composite material and preparation method thereof |
| CN101624457A (en) * | 2008-07-09 | 2010-01-13 | 北京理工大学 | Environmental protection based red mud combination modification synergism fire-retardant polyethylene |
-
2010
- 2010-12-15 CN CN201010587825XA patent/CN102050984A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN1068836A (en) * | 1992-07-17 | 1993-02-10 | 保定市裕南工程处阳台封闭材料厂 | A kind of composition that contains waste or used plastics |
| CN1369515A (en) * | 2001-02-16 | 2002-09-18 | 王林元 | Process for treating colour of red clay-plastic section |
| CN101235174A (en) * | 2008-02-26 | 2008-08-06 | 上海大学 | Environmental protection halogen-free anti-flaming polypropylene composite material and preparation method thereof |
| CN101624457A (en) * | 2008-07-09 | 2010-01-13 | 北京理工大学 | Environmental protection based red mud combination modification synergism fire-retardant polyethylene |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276919A (en) * | 2011-08-08 | 2011-12-14 | 中山市点石塑胶有限公司 | Flame-retardant polypropylene composite material and preparation method thereof |
| CN102276919B (en) * | 2011-08-08 | 2013-01-16 | 中山市点石塑胶有限公司 | Flame-retardant polypropylene composite material and preparation method thereof |
| CN102746562A (en) * | 2012-07-31 | 2012-10-24 | 王鸿 | Window material, preparing method and application thereof |
| CN102766290A (en) * | 2012-07-31 | 2012-11-07 | 王鸿 | Hot pressed plate and production method and application thereof |
| WO2014019419A1 (en) * | 2012-07-31 | 2014-02-06 | Wang Hong | Window material and preparation method thereof |
| CN102766290B (en) * | 2012-07-31 | 2014-07-09 | 王鸿 | Hot pressed plate and production method and application thereof |
| US9902832B2 (en) | 2013-01-22 | 2018-02-27 | Fluorchemie Gmbh Frankfurt | Inorganic, halogen-free flameproofing agent on the basis of chemically modified recarbonized red mud |
| RU2645511C2 (en) * | 2013-01-22 | 2018-02-21 | ФЛУОРХЕМИ ГмбХ ФРАНКФУРТ | Modified carbonized red sludge |
| US9908986B2 (en) | 2013-01-22 | 2018-03-06 | Fluorchemie Gmbh Frankfurt | Modified carbonized red mud |
| CN106753440A (en) * | 2016-12-29 | 2017-05-31 | 武汉工程大学 | The black paste produced in vitamin B6 industrial processes is in wood powder carbonization process as the application of fire retardant |
| CN106753440B (en) * | 2016-12-29 | 2018-11-06 | 武汉工程大学 | The black paste generated in vitamin B6 industrial processes is in wood powder carbonization process as the application of fire retardant |
| CN108219253A (en) * | 2018-01-19 | 2018-06-29 | 广西大学 | A kind of expansion type flame retardant of fire retardant low-density polyethylene |
| CN108484983A (en) * | 2018-04-19 | 2018-09-04 | 安徽工业大学 | A kind of red mud with high efficiency flame retardance-SILICA FUME compounded rubber filler and preparation method thereof |
| CN108484983B (en) * | 2018-04-19 | 2020-02-18 | 安徽工业大学 | Red mud-micro silicon powder composite rubber filler with efficient flame retardant property and preparation method thereof |
| CN109161075A (en) * | 2018-07-25 | 2019-01-08 | 山东理工大学 | It is a kind of using biomass fuel clinker as the composite material and preparation method of raw material |
| CN109161075B (en) * | 2018-07-25 | 2021-04-13 | 山东理工大学 | Composite material taking biomass combustion slagging as raw material and preparation method thereof |
| CN111117148A (en) * | 2020-01-03 | 2020-05-08 | 滨州学院 | Preparation method of red mud composite resin-based friction material |
| CN111117148B (en) * | 2020-01-03 | 2023-03-10 | 滨州学院 | Preparation method of red mud composite resin-based friction material |
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Application publication date: 20110511 |