CN107057237A - Tea saponin modification electrolytic manganese residues and its composite floor brick being made with waste or used plastics - Google Patents
Tea saponin modification electrolytic manganese residues and its composite floor brick being made with waste or used plastics Download PDFInfo
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- CN107057237A CN107057237A CN201710387423.7A CN201710387423A CN107057237A CN 107057237 A CN107057237 A CN 107057237A CN 201710387423 A CN201710387423 A CN 201710387423A CN 107057237 A CN107057237 A CN 107057237A
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- electrolytic manganese
- manganese residues
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
- E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
- E04F15/105—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials of organic plastics with or without reinforcements or filling materials
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Floor Finish (AREA)
- Processing Of Solid Wastes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of tea saponin modification electrolytic manganese residues, it is characterised in that：By 5~7wt% Tea Saponins, 2~5wt%NaOH and 88%~93wt% electrolytic manganese residues are constituted, and are made in the steps below：Electrolytic manganese residues and NaOH are added in high-speed mixer at 25 DEG C, stirred 6~7 minutes, Tea Saponin is added at 65 DEG C and is stirred under heating 5~6 minutes, tea saponin modification electrolytic manganese residues are obtained；Its composite floor brick being made with waste or used plastics, is prepared from the following raw materials in parts by weight：20~30 parts of waste vinylene chloride plastic, 70~80 parts of tea saponin modification electrolytic manganese residues, by blocks, molding of stirring, plasticate, cutting cut-parts.Electrolytic manganese residues surface nature is changed as lipophile by the present invention using Tea Saponin by hydrophily, its comixing compatibility with waste polyvinyl chloride, associativity is set to be greatly improved, the larger performance for improving composite floor brick, the filling number of electrolytic manganese residues in composite floor brick is added simultaneously, effectively reduces the cost of product.
Description
Technical field
The invention belongs to building material field, more particularly to a kind of Tea Saponin as waste vinylene chloride plastic filler
Modified electrolytic manganese residues and its composite floor brick being made with waste vinylene chloride plastic.
Background technology
At present, the industrial residue electrolytic manganese residues that China's chemical industry is discharged every year increase year by year, and these electrolytic manganese residues are current
In addition to electrolytic manganese slag brick, cement are produced except using, there is the storage ash field for being much stacked at electrolytic manganese residues, not only occupied soil
Ground, can also cause serious environmental pollution.In addition, it is growing with China's igelite production capacity and consumption figure, make
The plastic garbage yield for obtaining the formation of waste polyvinyl chloride plastics is more and more, causes serious " white pollution ".In addition, current use
It is generally that clay, china clay, stone material are made in the floor tile of the local ground laying such as public place and home dwelling, its production technology is answered
Miscellaneous, price is higher, and product still has certain defect in terms of water-proof skid-proof, warming heat conduction, sound absorption properties, comfortable foot feeling degree, suddenly treats one
Plant twice laid, the new material for reducing pollution, economizing on resources and solve problem.On the other hand in waste vinylene chloride plastic and electricity
Because electrolytic manganese residues belong to polarity inorganic matter, hydrophily in solution manganese slag Blending Processes, and waste vinylene chloride plastic belongs to nonpolar
Organic matter, lipophile, both physical form with it is far from it in chemical constitution, make to lack chemical bond force between the two, cause two
Inorganic filler disperses uneven, two-phase poor compatibility in above-mentioned organic matter when being mutually blended, so as to have influence on composite floor brick
Performance.
The content of the invention
It is an object of the invention to provide a kind of tea saponin modification electrolytic manganese residues and its with waste or used plastics be made it is compound
Plate brick, not only reduces the pollution of waste vinylene chloride plastic and industrial residue electrolytic manganese residues to environment, while the compound ground
Plate brick has simple production process, cheap, waterproof, the advantages of anti-skidding, heat conduction is warming, sound absorption properties are good, comfortable foot feeling degree is good.
The purpose of the present invention and solve its technical problem underlying using following technical scheme to realize：A kind of Tea Saponin
Modified electrolytic manganese residues, it is characterised in that by 5~7wt% Tea Saponins, 2~5wt%NaOH and 88%~93wt% electrolytic manganese residues groups
Into making in the steps below：
Electrolytic manganese residues and NaOH are added in high-speed mixer at 25 DEG C, stirs 6~7 minutes, tea is added at 65 DEG C
Saponin is stirred under heating 5~6 minutes, obtains tea saponin modification electrolytic manganese residues；
Described Tea Saponin is the class candy glucoside compound extracted in tea tree seed, is a kind of day of good performance
Right surfactant, the structure of Tea Saponin is as follows：
Described electrolytic manganese residues are the waste residues produced during producing electrolytic metal manganese powder with manganese carbonate ore through broken, powder
Gained, electrolytic manganese residues particle diameter≤700 μm after mill, screening.
The composite floor brick that described tea saponin modification electrolytic manganese residues are made with waste or used plastics, by the original of following parts by weight
Material is made：
20~30 parts of waste vinylene chloride plastic,
70~80 parts of tea saponin modification electrolytic manganese residues；
Make in the steps below：
A, waste vinylene chloride plastic is cleaned after, 1h is dried at a temperature of 120 DEG C, then be crushed to after below 4mm, obtains A
Product；
B, A product and tea saponin modification electrolytic manganese residues are stirred with homogenizer after, obtain B product；
C, B product are placed on three-roller open mill and are plasticated in flakes, then 120~160 DEG C of temperature, piece 0.5~0.8mm of thickness send
Enter and be molded on hot press, 150 DEG C~160 DEG C of molding temperature, pressure is 3.5MPa, 4~5 minutes time, obtains C product；
D, by C product press long 300mm, wide 300mm, thick 1.5mm standard size cutting cut-parts after get product.
The waste vinylene chloride plastic is the polrvinyl chloride product that industrial production and human lives are abandoned, selected from rain
Clothing, the tablecloth, curtain, power cable outermost layer epidermis, polychloroethylene pipes and section bar, battery jar.
The principle of the invention：The present invention utilizes the SiO containing 40~50wt% in electrolytic manganese residues2, it is under strong basicity environment
Sodium metasilicate is generated with NaOH, subsequent Tea Saponin generates Tea Saponin carboxylic acid sodium, last sodium metasilicate and Tea Saponin carboxylic acid sodium point with NaOH
Acid-base reaction occurs for the hydroxyl in son, generates coupled esters of silicon acis Tea Saponin sodium.
Specific reaction equation is as follows：
The first step：
Second step：
Tea Saponin molecular structure：
It is reduced to：(HO)11-R-COOH
3rd step：
Glycosyl in coupled esters of silicon acis Tea Saponin sodium structure has preferable hydrophily, and electrolytic manganese residues can be changed
Property, electrolytic manganese residues surface nature is changed as lipophile by hydrophily, modified electrolytic manganese residues have good in organic phase
Dispersive property, makes its comixing compatibility with waste vinylene chloride plastic, associativity be greatly improved, is added significantly to nothing
The filling number of machine filler electrolytic manganese residues, effectively reduces the cost of product.Meanwhile, coupled esters of silicon acis Tea Saponin sodium molecule
The carboxyl contained and alkali reaction generation carboxylic acid sodium, so as to produce powerful electronegative carboxylate group on carbonyl.Polychlorostyrene second
α carbon connection chlorine atom in alkene, shows stronger electropositive, it is sufficiently mixed with polyvinyl chloride raw material, in Tea Saponin esters of silicon acis
Oxygen atom more effective absorption can be produced by Van der Waals force between the α carbon of polyvinyl chloride, so as to produce different poly-
Van der Waals connection between vinyl chloride strand, realizes the intensity increase of igelite.Improve the property of composite floor brick
Energy.Dependency structure is as follows：
The invention has the characteristics that：
(1) present invention is modified using Tea Saponin to electrolytic manganese residues first, using in electrolytic manganese residues containing 40~
50wt% SiO2, it generates sodium metasilicate under strong basicity environment with NaOH, and subsequent Tea Saponin generates Tea Saponin carboxylic acid with NaOH
With the hydroxyl in Tea Saponin carboxylic acid sodium molecule acid-base reaction occurs for sodium, last sodium metasilicate, generates coupled esters of silicon acis Tea Saponin sodium.
Glycosyl in the structure has preferable hydrophily, and electrolytic manganese residues can be modified, by electrolytic manganese residues surface nature by hydrophilic
Sexually revise as lipophile, modified electrolytic manganese residues have good dispersive property in organic phase, make itself and waste polyvinyl chloride
The comixing compatibilities of plastics, associativity are greatly improved, and are added significantly to the filling number of inorganic filler electrolytic manganese residues, have
The cost for reducing product of effect.Meanwhile, the carboxyl that coupled esters of silicon acis Tea Saponin sodium molecule contains and alkali reaction generation carboxylic acid
Sodium, so as to produce powerful electronegative carboxylate group on carbonyl.In polyvinyl chloride α carbon connection chlorine atom, show compared with
Strong electropositive, it is sufficiently mixed with polyvinyl chloride raw material, the α carbon that the oxygen atom in Tea Saponin esters of silicon acis can be with polyvinyl chloride
Between more effective absorption is produced by Van der Waals force so that the Van der Waals produced between different polyvinyl chloride strands connects
Connect, realize the intensity increase of igelite, improve the performance of composite floor brick.
(2) waste vinylene chloride plastic that the present invention is abandoned using industrial production and human lives is electrolysed with industrial residue
Manganese slag is primary raw material, using suitable preparation method, composite floor brick is made, waste or used plastics and industrial residue pair are both alleviated
The pollution of environment, adds new material for architectural engineering again.
Embodiment
Embodiment 1：
Tea saponin modification electrolytic manganese residues are made in the steps below：
93Kg electrolytic manganese residues and 2KgNaOH are added in high-speed mixer at 25 DEG C, stirred 6~7 minutes, at 65 DEG C
Add 5Kg Tea Saponins to be stirred under heating 5~6 minutes, obtain tea saponin modification electrolytic manganese residues.
Composite floor brick is made in the steps below：
A, by 200Kg waste vinylene chloride plastics clean after, 1h is dried at a temperature of 120 DEG C, then be crushed to below 4mm
Afterwards, A product are obtained；
B, A product and 800Kg tea saponin modification electrolytic manganese residues are stirred with homogenizer after, obtain B product；
C, B product are placed on three-roller open mill and are plasticated in flakes, then 120~160 DEG C of temperature, piece 0.5~0.8mm of thickness send
Enter and be molded on hot press, 150 DEG C~160 DEG C of molding temperature, pressure is 3.5MPa, 4~5 minutes time, obtains C product；
D, by C product press long 300mm, wide 300mm, thick 1.5mm standard size cutting cut-parts after get product.
With the identical material prescription of embodiment 1, technological process, technological parameter under the conditions of, it is even using conventional silane
The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to electrolytic manganese residues, and reproduction is multiple
Floor tile is closed, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry row
Industry proposed standard (HG/T 3747.1-2004) is performed, and the effect to modified electrolytic manganese residues is contrasted, its testing result such as table 1
Shown in~7.
The composite floor brick Hardness results of table 1
The composite floor brick tensile strength testing result of table 2
The composite floor brick tearing strength testing result of table 3
The composite floor brick wearability testing result of table 4
The composite floor brick heated dimensions of table 5 change performance test results
The composite floor brick fire resistance testing result of table 6
The composite floor brick brittleness temperature testing result of table 7
From table 1~7 as can be seen that the present embodiment finished product correlated performance detection result reaches that state's public places in Nan Chong and family live
The floor tile standard of the place such as residence ground laying, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry proposed standard
(HG/T3747.1-2004) conventional silane coupler, titanate coupling agent, Aluminate, and under the conditions of same recipe are superior to
The coupling agents such as coupling agent, stearic acid to the modified effect of electrolytic manganese residues, make its comixing compatibility with waste vinylene chloride plastic,
Associativity is greatly improved, and larger improves the performance of composite floor brick, while adding inorganic filler electrolytic manganese residues
Filling number, effectively reduce the cost of product.The target of the present invention is realized.
Embodiment 2：
Tea saponin modification electrolytic manganese residues are made in the steps below：
92Kg electrolytic manganese residues and 4KgNaOH are added in high-speed mixer at 25 DEG C, stirred 6~7 minutes, at 65 DEG C
Add 6Kg Tea Saponins to be stirred under heating 5~6 minutes, obtain tea saponin modification electrolytic manganese residues.
Composite floor brick is made in the steps below：
A, by 250Kg waste vinylene chloride plastics clean after, 1h is dried at a temperature of 120 DEG C, then be crushed to below 4mm
Afterwards, A product are obtained；
B, A product and 750Kg tea saponin modification electrolytic manganese residues are stirred with homogenizer after, obtain B product；
C, B product are placed on three-roller open mill and are plasticated in flakes, then 120~160 DEG C of temperature, piece 0.5~0.8mm of thickness send
Enter and be molded on hot press, 150 DEG C~160 DEG C of molding temperature, pressure is 3.5MPa, 4~5 minutes time, obtains C product；
D, by C product press long 300mm, wide 300mm, thick 1.5mm standard size cutting cut-parts after get product.
With the identical material prescription of embodiment 2, technological process, technological parameter under the conditions of, it is even using conventional silane
The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to electrolytic manganese residues, and reproduction is multiple
Floor tile is closed, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry row
Industry proposed standard (HG/T 3747.1-2004) is performed, and the effect to modified electrolytic manganese residues is contrasted, its testing result such as table 8
Shown in~14.
The composite floor brick Hardness results of table 8
The composite floor brick tensile strength testing result of table 9
The composite floor brick tearing strength testing result of table 10
The composite floor brick wearability testing result of table 11
The composite floor brick heated dimensions of table 12 change performance test results
The composite floor brick fire resistance testing result of table 13
The composite floor brick brittleness temperature testing result of table 14
From table 8~14 as can be seen that the present embodiment finished product correlated performance detection result reaches state's public places in Nan Chong and family
The floor tile standard of the place such as house ground laying, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry recommends mark
Accurate (HG/T3747.1-2004), and it is superior under the conditions of same recipe conventional silane coupler, titanate coupling agent, aluminic acid
The coupling agents such as ester coupling agent, stearic acid make it compatible with the blending of waste vinylene chloride plastic the modified effect of electrolytic manganese residues
Property, associativity are greatly improved, the larger performance for improving composite floor brick, while adding inorganic filler electrolytic manganese
The filling number of slag, effectively reduces the cost of product.The target of the present invention is realized.
Embodiment 3：
Tea saponin modification electrolytic manganese residues are made in the steps below：
88Kg electrolytic manganese residues and 5KgNaOH are added in high-speed mixer at 25 DEG C, stirred 6~7 minutes, at 65 DEG C
Add 7Kg Tea Saponins to be stirred under heating 5~6 minutes, obtain tea saponin modification electrolytic manganese residues.
Composite floor brick is made in the steps below：
A, by 300Kg waste vinylene chloride plastics clean after, 1h is dried at a temperature of 120 DEG C, then be crushed to below 4mm
Afterwards, A product are obtained；
B, A product and 700Kg tea saponin modification electrolytic manganese residues are stirred with homogenizer after, obtain B product；
C, B product are placed on three-roller open mill and are plasticated in flakes, then 120~160 DEG C of temperature, piece 0.5~0.8mm of thickness send
Enter and be molded on hot press, 150 DEG C~160 DEG C of molding temperature, pressure is 3.5MPa, 4~5 minutes time, obtains C product；
D, by C product press long 300mm, wide 300mm, thick 1.5mm standard size cutting cut-parts after get product.
With the identical material prescription of embodiment 3, technological process, technological parameter under the conditions of, it is even using conventional silane
The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to electrolytic manganese residues, and reproduction is multiple
Floor tile is closed, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry row
Industry proposed standard (HG/T 3747.1-2004) is performed, and the effect to modified electrolytic manganese residues is contrasted, its testing result such as table
Shown in 15~21.
The composite floor brick Hardness results of table 15
The composite floor brick tensile strength testing result of table 16
The composite floor brick tearing strength testing result of table 17
The composite floor brick wearability testing result of table 18
The composite floor brick heated dimensions of table 19 change performance test results
The composite floor brick fire resistance testing result of table 20
The composite floor brick brittleness temperature testing result of table 21
From table 15~21 as can be seen that the present embodiment finished product correlated performance detection result reaches state's public places in Nan Chong and family
The floor tile standard of the place such as house ground laying, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry recommends mark
Accurate (HG/T3747.1-2004), and it is superior under the conditions of same recipe conventional silane coupler, titanate coupling agent, aluminic acid
The coupling agents such as ester coupling agent, stearic acid make it compatible with the blending of waste vinylene chloride plastic the modified effect of electrolytic manganese residues
Property, associativity are greatly improved, the larger performance for improving composite floor brick, while adding inorganic filler electrolytic manganese
The filling number of slag, effectively reduces the cost of product.The target of the present invention is realized.
In summary, the composite floor brick that the present invention makes reaches the local ground paving such as state's public places in Nan Chong and home dwelling
If floor tile standard, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry proposed standard (HG/T3747.1-
2004) conventional silane coupler, titanate coupling agent, aluminate coupling agent, stearic acid etc., are superior under the conditions of same recipe
Coupling agent is to the modified effects of electrolytic manganese residues, while the product has simple production process, cheap, water-proof skid-proof, heat conduction
The advantages of warming, sound absorption properties are good, comfortable foot feeling degree is good, with preferable social benefit and market prospects.
Claims (4)
1. a kind of tea saponin modification electrolytic manganese residues, it is characterised in that：By 5~7wt% Tea Saponins, 2~5wt%NaOH and 88%~
93wt% electrolytic manganese residues are constituted, and are made in the steps below：
Electrolytic manganese residues and NaOH are added in high-speed mixer at 25 DEG C, stirs 6~7 minutes, Tea Saponin is added at 65 DEG C
It is stirred under heating 5~6 minutes, obtains tea saponin modification electrolytic manganese residues；
Described Tea Saponin is the class candy glucoside compound extracted in tea tree seed, is a kind of natural table of good performance
Face activating agent, the structure of Tea Saponin is as follows：
。
2. tea saponin modification electrolytic manganese residues as claimed in claim 1, it is characterised in that：Described electrolytic manganese residues are to use manganese carbonate
The waste residue produced during ore deposit production electrolytic metal manganese powder gained after broken, grinding, screening, the electrolytic manganese residues particle diameter≤
700μm。
3. the composite floor brick that tea saponin modification electrolytic manganese residues as claimed in claim 1 or 2 are made with waste or used plastics, its feature
It is：It is prepared from the following raw materials in parts by weight：
20~30 parts of waste vinylene chloride plastic,
70~80 parts of tea saponin modification electrolytic manganese residues；
Make in the steps below：
A, waste vinylene chloride plastic is cleaned after, 1h is dried at a temperature of 120 DEG C, then be crushed to after below 4mm, obtains A product；
B, A product and tea saponin modification electrolytic manganese residues are stirred with homogenizer after, obtain B product；
C, B product are placed on three-roller open mill and are plasticated in flakes, 120~160 DEG C of temperature, the 8mm of piece thickness 0.5~0. is then fed into heat
It is molded on press, 150 DEG C~160 DEG C of molding temperature, pressure is 3.5MPa, 4~5 minutes time, obtains C product；
D, by C product press long 300mm, wide 300mm, thick 1.5mm standard size cutting cut-parts after get product.
4. the composite floor brick that tea saponin modification electrolytic manganese residues as claimed in claim 3 are made with waste or used plastics, its feature exists
In：The waste vinylene chloride plastic is the polrvinyl chloride product that industrial production and human lives are abandoned, selected from raincoat, platform
Cloth, curtain, power cable outermost layer epidermis, polychloroethylene pipes and section bar, battery jar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710387423.7A CN107057237A (en) | 2017-05-27 | 2017-05-27 | Tea saponin modification electrolytic manganese residues and its composite floor brick being made with waste or used plastics |
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|---|---|---|---|
| CN201710387423.7A CN107057237A (en) | 2017-05-27 | 2017-05-27 | Tea saponin modification electrolytic manganese residues and its composite floor brick being made with waste or used plastics |
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| CN107057237A true CN107057237A (en) | 2017-08-18 |
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ID=59610763
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| CN201710387423.7A Pending CN107057237A (en) | 2017-05-27 | 2017-05-27 | Tea saponin modification electrolytic manganese residues and its composite floor brick being made with waste or used plastics |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430371A (en) * | 2020-11-18 | 2021-03-02 | 重庆前跃环境治理有限公司 | Superfine manganese slag modified PVC composite material, preparation method and application |
| CN114315281A (en) * | 2022-01-12 | 2022-04-12 | 广西汇元锰业有限责任公司 | Method for preparing foam concrete brick by using electrolytic manganese dioxide waste residue |
| CN114716749A (en) * | 2022-03-23 | 2022-07-08 | 贵阳伟佳塑料有限公司 | Preparation method of plastic drain pipe filled with electrolytic manganese residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114315281A (en) * | 2022-01-12 | 2022-04-12 | 广西汇元锰业有限责任公司 | Method for preparing foam concrete brick by using electrolytic manganese dioxide waste residue |
| CN114716749A (en) * | 2022-03-23 | 2022-07-08 | 贵阳伟佳塑料有限公司 | Preparation method of plastic drain pipe filled with electrolytic manganese residues |
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Application publication date: 20170818 |