CN102070815A - Dealkalized red mud-containing flame-retardant polyvinyl plastic and preparation method thereof - Google Patents
Dealkalized red mud-containing flame-retardant polyvinyl plastic and preparation method thereof Download PDFInfo
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- CN102070815A CN102070815A CN 201010606051 CN201010606051A CN102070815A CN 102070815 A CN102070815 A CN 102070815A CN 201010606051 CN201010606051 CN 201010606051 CN 201010606051 A CN201010606051 A CN 201010606051A CN 102070815 A CN102070815 A CN 102070815A
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Abstract
The invention relates to dealkalized red mud-containing flame-retardant polyvinyl plastic and a preparation method thereof, and belongs to the technical fields of dealkalization and comprehensive utilization of red mud and flame-retardant plastic. Polyethylene and an in-situ dealkalizing agent are used as resin bases, and the red mud is used as a flame retardant. The method comprises the following steps of: crushing the red mud; drying; grinding and sieving; adding the red mud into an internal mixer with the polyethylene and the in-situ dealkalizing agent for melting and internal mixing; and machine-shaping with a flat vulcanizing machine to obtain a flame-retardant polyvinyl plastic finished product, wherein the plastic has smooth appearance, the pH value is between 9 and 11, and the limiting oxygen index ranges from 23 to 31 percent. The polyvinyl plastic prepared by the method is suitable for fire disaster safety protection in important public places in the fields of electronic appliances, building materials and traffic; a dealkalization process used for the red mud serving as the flame retardant is simplified by in-situ dealkalization; the in-situ dealkalizing agent can effectively reduce the alkalinity of the red mud, improve the flame-retardant effect and improve the compatibility between the red mud and the polyethylene base; and the polyvinyl plastic is low in cost and causes small damage to environment.
Description
Technical field
The present invention relates to a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud and preparation method thereof, belong to dealkalize, comprehensive utilization and the flame retardant plastics technical field of red mud.
Background technology
Red mud is the waste residue that produces in aluminum oxide production process, takes on a red color because of containing a large amount of ferric oxide, so be called as red mud.The annual red mud amount that produces surpasses 6,000,000 tons in China's aluminum oxide production process, all stores up in the open, not only takies a large amount of soils, and is present in alkali in the red mud to underground infiltration, causes the pollution of body of groundwater and soil, is endangering ecotope.Therefore, the comprehensive utilization of research red mud is significant.
The oxide compound and the multiple useful metal element that contain reproducible utilization in the red mud become the basis of red mud regeneration.Contain SiO in the red mud
2, CaO, Fe
2O
3, Al
2O
3, MgO, Na
2O, K
2Metal oxides such as O, wherein the red mud that exists for of elements such as Si, Al, Mg is used as compound flame retardant condition is provided.In plastics industry, red mud is mainly as the plastic functional filler at present.
A large amount of alkaline components mainly contain Na in the red mud
2O and K
2O etc., the existence of these alkaline components, the Tripyrophosphoric acid that the phosphonium flame retardant that neutralization and red mud is composite discharges weakens the condensed phase fire retardation that it is dehydrated into charcoal.Therefore will carry out dealkalize to red mud handles.The method of red mud dealkalization processing at present is a lot, its objective is and weakens the pollution of red mud to environment water.Dealkalization method mainly contains: (1) Wingdale hydrothermal method.Under high pressure add the alkali in the lime exsolution red mud; (2) limestone sintering method red mud dealkalization.Promptly in raw material, add a certain amount of lime, in grog, add a certain amount of soda ash, under normal pressure, deviate from the alkali in the red mud; (3) acid leaching process.This method is to utilize concentrated acid dipping red mud, deviates from the alkaline components in the red mud; (4) salt lixiviation process.Adopt the Na in the inorganic salt dissolving red mud
2O; (5) three industrial wastes neutralisation.Utilize in the waste water,waste gas and industrial residue and red mud basicity; (6) lime soda ash sintering process.Lime, soda ash, Bayer process red mud are mixed, and sintering is used the alkali in the weakly alkaline solution exsolution red mud at a certain temperature; (7) bacterium lixiviation process.The alkali in the red mud is leached in the direct or indirect effect of the rotten bacterium enzyme of utilization metabolism; (8) film takes off the sodium technology.
Summary of the invention
The objective of the invention is to propose a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud and preparation method thereof in order to reduce in the prior art the serious problem of environmental pollution when using red mud as fire retardant.
The objective of the invention is to be achieved through the following technical solutions.
A kind of flame-retardant polyethylene plastic that contains the dealkalize red mud of the present invention, with polyethylene and original position dealkalize agent as resin base, with red mud as fire retardant; And in the total mass of vinyon, each several part quality percentage composition is:
Polyethylene 20%～40%
Red mud 50%～70%
Original position dealkalize agent 4%～16%
Used red mud is preferably used Bayer process red mud according to the production technique difference of aluminum oxide.
Above-mentioned original position dealkalize agent is a kind of in maleic anhydride grafted polyethylene, ethylene-vinyl acetate copolymer or the ethylene-acrylic acid copolymer; Wherein, the percentage of grafting of maleic anhydride grafted polyethylene is 5%～10%; Vinyl quality percentage composition is 28%～45% in the ethylene-vinyl acetate copolymer; Acrylic acid quality percentage composition is 9.7%～12.5% in the ethylene-acrylic acid copolymer; Above-mentioned substance can also be as expanding material, and original position dealkalize agent is preferably ethylene-vinyl acetate copolymer.
A kind of preparation method who contains the flame-retardant polyethylene plastic of dealkalize red mud of the present invention, step is:
1) red mud is pulverized, dry, ground 400～1000 mesh sieves;
2) red mud, polyethylene and the original position dealkalize agent after will sieving joins melt blending processing in the mixing roll, uses vulcanizing press machine-shaping then, obtains the flame-retardant polyethylene plastic finished product, this plastics smooth in appearance;
Above-mentioned steps 2) in, the mixing roll processing temperature is 140～150 ℃; Vulcanizing press machine-shaping temperature is 120～130 ℃, heat-up time 4～8min, pressure 10～20MPa.
The pH value of the flame-retardant polyethylene plastic of method for preparing is 9～11, and its limiting oxygen index(LOI) scope is 23%～31%, and its mechanical property, processing characteristics and thermal stability are good.
The temperature of Bayer process red mud thermal weight loss 1% and 5% correspondence is respectively 240 ℃ and 330 ℃, and Bayer process red mud has good thermostability, can satisfy the melt blending process requirements of general-purpose plastics; The release of weightless corresponding respectively red mud planar water of two sections of thermogravimetric curves and intercrystalline water, fluid loss is 11.4% in the whole thermal decomposition process, it is fire-retardant to help absorbing heat; When temperature rose to 700 ℃, level of residue was 88.6%, and the residue that contains the ignition-proof element oxide compound helps heat-insulating flame-retardant.
Beneficial effect
The red mud flame-retardant polyethylene plastic of the present invention's preparation is applicable to the fire safety evaluating protection of electronic apparatus, material of construction, the important public place of field of traffic; The dealkalize treatment process that red mud uses as fire retardant has been simplified in the original position dealkalize; Original position dealkalize agent can effectively reduce the alkalescence of red mud, improves flame retardant effect, and can improve the consistency between red mud and polyethylene matrix; Cost is low and red mud is little to the harm of environment.
Embodiment
Embodiment 1
1) the 150g red mud is pulverized, dry, ground 550 mesh sieves;
2) red mud, 70g polyethylene and the 30g maleic anhydride grafted polyethylene after will sieving joins melt blending processing in the mixing roll, uses vulcanizing press machine-shaping then, obtains the flame-retardant polyethylene plastic finished product, this plastics smooth in appearance;
Above-mentioned steps 2) poly melting index is 8g/10min in; The percentage of grafting of maleic anhydride grafted polyethylene is 7.5%;
Above-mentioned steps 2) in, the mixing roll processing temperature is 150 ℃; Vulcanizing press machine-shaping temperature is 120 ℃, heat-up time 8min, pressure 20MPa;
The pH value of the flame-retardant polyethylene plastic of method for preparing is 9.5, and its limiting oxygen index(LOI) is 26.3%, and its tensile strength is 10.5MPa, and elongation at break is 30%, and processing characteristics and thermal stability are good.
Embodiment 2
1) the 150g red mud is pulverized, dry, ground 550 mesh sieves;
2) red mud, 70g polyethylene and the 30g ethylene-vinyl acetate copolymer after will sieving joins melt blending processing in the mixing roll, uses vulcanizing press machine-shaping then, obtains flame-retardant polyethylene plastic, this plastics smooth in appearance;
Above-mentioned steps 2) poly melting index is 8g/10min in; Vinyl quality percentage composition is 28% in the ethylene-vinyl acetate copolymer.
Above-mentioned steps 2) in, the mixing roll processing temperature is 150 ℃; Vulcanizing press machine-shaping temperature is 120 ℃, heat-up time 8min, pressure 20MPa.
The pH value of the flame-retardant polyethylene plastic of method for preparing is 10.0, and its limiting oxygen index(LOI) is 25.8%, and its tensile strength is 9.2MPa, and elongation at break is 27%, and processing characteristics and thermal stability are good.
Embodiment 3
1) the 150g red mud is pulverized, dry, ground 550 mesh sieves;
2) red mud, 70g polyethylene and the 30g ethylene-acrylic acid copolymer after will sieving joins melt blending processing in the mixing roll, uses vulcanizing press machine-shaping then, obtains flame-retardant polyethylene plastic, this plastics smooth in appearance;
Above-mentioned steps 2) poly melting index is 8g/10min in; Acrylic acid quality percentage composition is 10.3% in the ethylene-acrylic acid copolymer.
Above-mentioned steps 2) in, the mixing roll processing temperature is 150 ℃; Vulcanizing press machine-shaping temperature is 120 ℃, heat-up time 8min, pressure 20MPa.
The pH value of the flame-retardant polyethylene plastic of method for preparing is 9.8, and its limiting oxygen index(LOI) is 25.6%, and its tensile strength is 13.2MPa, and elongation at break is 38%, and processing characteristics and thermal stability are good.
Comparative Examples
1) the 150g red mud is pulverized, dry, ground 550 mesh sieves;
2) red mud after will sieving and 100g polyethylene join melt blending processing in the mixing roll, use vulcanizing press machine-shaping then, obtain flame-retardant polyethylene plastic, this plastics smooth in appearance;
Above-mentioned steps 2) poly melting index is 8g/10min in.
Above-mentioned steps 2) in, the mixing roll processing temperature is 150 ℃; Vulcanizing press machine-shaping temperature is 120 ℃, heat-up time 8min, pressure 20MPa.
The pH value of the flame-retardant polyethylene plastic of method for preparing is 12.8, and its limiting oxygen index(LOI) is 21.7%, and its tensile strength is 7.2MPa, and elongation at break is 22%, and processing characteristics and thermostability are relatively poor.
Claims (8)
1. flame-retardant polyethylene plastic that contains the dealkalize red mud is characterized in that: with polyethylene and original position dealkalize agent as resin base, with red mud as fire retardant; And in the total mass of vinyon, each several part quality percentage composition is:
Polyethylene 20%～40%
Red mud 50%～70%
Original position dealkalize agent 4%～16%
Used red mud is a Bayer process red mud; Original position dealkalize agent is a kind of in maleic anhydride grafted polyethylene, ethylene-vinyl acetate copolymer or the ethylene-acrylic acid copolymer.
2. a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud according to claim 1 is characterized in that: the percentage of grafting of maleic anhydride grafted polyethylene is 5%～10%.
3. a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud according to claim 1 is characterized in that: vinyl quality percentage composition is 28%～45% in the ethylene-vinyl acetate copolymer.
4. a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud according to claim 1 is characterized in that: acrylic acid quality percentage composition is 9.7%～12.5% in the ethylene-acrylic acid copolymer.
5. a kind of flame-retardant polyethylene plastic that contains the dealkalize red mud according to claim 1 is characterized in that: original position dealkalize agent is preferably ethylene-vinyl acetate copolymer.
6. preparation method who contains the flame-retardant polyethylene plastic of dealkalize red mud is characterized in that step is:
1) red mud is pulverized, dry, ground 400～1000 mesh sieves;
2) red mud, polyethylene and the original position dealkalize agent after will sieving joins melt blending processing in the mixing roll, uses vulcanizing press machine-shaping then, obtains the flame-retardant polyethylene plastic finished product, this plastics smooth in appearance;
The pH value of the flame-retardant polyethylene plastic of method for preparing is 9～11, and its limiting oxygen index(LOI) scope is 23%～31%, and its mechanical property, processing characteristics and thermal stability are good.
7. a kind of preparation method who contains the flame-retardant polyethylene plastic of dealkalize red mud according to claim 6 is characterized in that: the mixing roll processing temperature is 140～150 ℃.
8. a kind of preparation method who contains the flame-retardant polyethylene plastic of dealkalize red mud according to claim 6 is characterized in that: vulcanizing press machine-shaping temperature is 120～130 ℃, heat-up time 4～8min, pressure 10～20MPa.
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| CN 201010606051 CN102070815A (en) | 2010-12-15 | 2010-12-15 | Dealkalized red mud-containing flame-retardant polyvinyl plastic and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108239323A (en) * | 2017-11-30 | 2018-07-03 | 贵阳兴塑科技股份有限公司 | A kind of method of ardealite and red mud filling PE drainpipes |
| CN111333911A (en) * | 2018-12-19 | 2020-06-26 | 杨建强 | Red mud treating agent based on grafted wax and preparation method and application thereof |
| RU2728137C2 (en) * | 2016-03-15 | 2020-07-28 | Флюорхеми Гмбх Франкфурт | Composition containing modified red mud with low content of chromates, and a method for production thereof |
| CN114230887A (en) * | 2020-09-09 | 2022-03-25 | 贵州大学 | Red mud/crosslinked polyethylene composite material for pipes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 CN 201010606051 patent/CN102070815A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2645511C2 (en) * | 2013-01-22 | 2018-02-21 | ФЛУОРХЕМИ ГмбХ ФРАНКФУРТ | Modified carbonized red sludge |
| 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 |
| US9908986B2 (en) | 2013-01-22 | 2018-03-06 | Fluorchemie Gmbh Frankfurt | Modified carbonized red mud |
| RU2728137C2 (en) * | 2016-03-15 | 2020-07-28 | Флюорхеми Гмбх Франкфурт | Composition containing modified red mud with low content of chromates, and a method for production thereof |
| US10766812B2 (en) | 2016-03-15 | 2020-09-08 | Fluorchemie Gmbh Frankfurt | Composition containing modified chromate-deficient red mud and method for producing same |
| US11161784B2 (en) | 2016-03-15 | 2021-11-02 | Fluorchemie Gmbh Frankfurt | Material and production thereof for use as a storage medium in a sensitive energy storage system in the low-, medium- or high-temperature range |
| CN108239323A (en) * | 2017-11-30 | 2018-07-03 | 贵阳兴塑科技股份有限公司 | A kind of method of ardealite and red mud filling PE drainpipes |
| 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 |
| CN111333911A (en) * | 2018-12-19 | 2020-06-26 | 杨建强 | Red mud treating agent based on grafted wax and preparation method and application thereof |
| CN114230887A (en) * | 2020-09-09 | 2022-03-25 | 贵州大学 | Red mud/crosslinked polyethylene composite material for pipes |
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Application publication date: 20110525 |