CN106590066A - Rubber packing preparation method, rubber packing and compound rubber - Google Patents
Rubber packing preparation method, rubber packing and compound rubber Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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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
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Abstract
The invention discloses a rubber packing preparation method and rubber packing, wherein the method comprises the steps of (1) washing residue after extracting aluminum from coal ash with water, and grinding by a wet method, so as to obtain ground residue after extracting aluminum from coal ash; (2) adding water and a surface modifying agent in the ground residue after extracting aluminum from coal ash for surface modification, so as to obtain modified residue after extracting aluminum from coal ash; (3) drying and scattering the modified residue after extracting aluminum from coal ash, so as to obtain the rubber packing; the surface modifying agent is one or more of stearic acid, sodium stearate, oleic acid and sodium oleate; the invention also discloses compound rubber made from the packing. The preparation method provided by the invention is simple, the residue after extracting aluminum from coal ash is modified by using the surface modifying agent, so as to improve the compatibility thereof with a plastic substrate, not only can waste be changed into wealth, but also the pollution to environment by direct emission of the residue after extracting aluminum from coal ash can be avoided, the prepared rubber packing can be added heavily, and the cost of rubber products is reduced on the basis of not reducing the performance of the rubber products, thereby improving economic benefit.
Description
Technical field
The invention belongs to rubber materials, more particularly to a kind of preparation method of gum filler, gum filler and compounded rubber.
Background technology
Flyash be thermal power plant produce industrial solid castoff, be the larger industrial residue of the current discharge capacity of China it
One.With the development of power industry, the flyash discharge capacity of coal-burning power plant of China increases year by year.The discharge of flyash had both caused soil
Environmental pollution and the environmental destructions such as ground, water body and air, waste the precious resources as silicate material again, are badly in need of out
High value added product is sent out, in addition efficient utilization, to promote China's economizing type recycling economy development.If to total utilization of PCA
Research and process are not gone into overdrive, it will bring immeasurable consequence to production of energy, comprehensive utilization of resources and environmental conservation.
The composition of various places flyash is different, for Al2O3The high flyash of content, typically adopts acid system or alkaline process by aluminum from flyash
Extract, make full use of regenerated resources, improve the comprehensive utilization value of flyash.Residue of aluminum-extracted pulverized fuel ash has granule thin
The high feature of little, short texture, activity, using with obvious technical advantage and economic advantages in macromolecular material.At present
The utilization of residue of aluminum-extracted pulverized fuel ash is concentrated mainly on construction material aspect, and feature is that usage amount is big, but added value is low, from resource profit
It is a kind of waste for property.
Most widely used particulate filler is mainly white carbon black, white carbon etc. in rubber industry, and this kind of filler is because of production cost
It is high and price is also high.With a large amount of uses of rubber and its being continuously increased for consumption figure, the demand of filler is consequently increased.
CN102532955A is disclosed《A kind of preparation method of coveredwith nanometer calcium carbonate flyash micropowder》.Powder of the method to discard
Coal ash is raw material, by superfine grinding, activation, then to its surface with nano-calcium carbonate coated and chemical modification, coupling at
Reason, obtains that the coveredwith nanometer calcium carbonate flyash micropowder that precipitated calcium carbonate is filled in rubber and plastic can be substituted.
Preferably 32 μm of the fineness of pulverized-coal ash of superfine grinding, residue on sieve≤8wt% in the patent；Modified-reaction temperature is 70 DEG C～90 DEG C,
The flyash micropowder product granularity that the method is obtained is thicker, and technique is more complicated.The A of CN 102775816 are disclosed《Acid system is carried
Flyash waste after aluminum be modified prepare gum filler method》.Acid system is proposed the flyash waste drip washing after aluminum extremely by the method
Dry, pulverize after neutrality to 300 mesh, add organic modifiers, mixed at high speed, grinding are gum filler after ageing.The method
Although the cost of rubber can be reduced, solid waste coal ash residue of aluminum-extracted can be effectively utilized again, reduce ecological ring
The pollution in border, but the gum filler granularity for obtaining is larger, only reaches 300 mesh, and to rubber good strengthening action can not be played.
The content of the invention
It is an object of the invention to provide a kind of preparation method of gum filler and gum filler, the gum filler is to utilize
Residue of aluminum-extracted pulverized fuel ash is prepared, and has the good compatibility with rubber matrix, the good dispersion in rubber matrix.
Further object is that providing a kind of compounded rubber, the compounded rubber performance is good.
To realize the one side of the object of the invention, the invention provides a kind of preparation method of gum filler, employing
Technical scheme is as follows：
A kind of preparation method of gum filler, comprises the following steps：
(1) residue of aluminum-extracted pulverized fuel ash is washed and wet method is levigate, obtain fine-ground fly-ash residue of aluminum-extracted；
(2) add water and surface modifier to carry out surface in the fine-ground fly-ash residue of aluminum-extracted obtained to step (1) to be modified,
Obtain modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler；
Wherein, the surface modifier is the group of any one or more in stearic acid, sodium stearate, Oleic acid and enuatrol
Close.
In the present invention, described residue of aluminum-extracted pulverized fuel ash refers to that flyash extracts the residue formed after aluminium oxide.Powder
Coal ash residue of aluminum-extracted is it is known in the art, can be obtained by conventional method.For example, can by CN102153117A,
The methods such as CN101870489A, CN102145904A, CN102145905A obtain residue of aluminum-extracted pulverized fuel ash.For example
Sour molten disclosed in CN102145905A puies forward aluminum technique, and it is incorporated into by way of reference in the application.Specifically, it is described
The preparation method of residue of aluminum-extracted pulverized fuel ash may comprise steps of：
1), magnetically separating and removing ion from fly ash:Flyash is size-reduced to be reached below 100 mesh, add water be made into solid content for 20～
The slurry of 40wt%, on vertical ring magnetic separator magnetic separation, magnetic separation field intensity 1.0～2.0 ten thousand GS are carried out；Slurry Jing solid-liquids after magnetic separation
The filter cake that solid content is 25～50wt% is obtained after separation；
2), acid is molten:Filter cake after magnetic separation is placed in acid-resistant reacting kettle to carry out hydrochloric acid acid molten, concentration of hydrochloric acid is 20～
35wt%, HCl and the mol ratio of aluminium oxide in flyash are 4 in hydrochloric acid:1～9:1, leaching temperature is 100 DEG C～200 DEG C, molten
Go out 0.1～2.5MPa of pressure, dissolution time is 0.5h～4h；Preferably, concentration of hydrochloric acid be 20～30wt%, in hydrochloric acid HCl with
The mol ratio of aluminium oxide is 4.5 in flyash:1～9:1, leaching temperature is 130 DEG C～150 DEG C, dissolution pressure 0.3～
1.0MPa, dissolution time is 1.5h～2.5h；The molten rear product Jing solid-liquid separation of acid, obtains the residue of aluminum-extracted pulverized fuel ash.
Above-mentioned steps 2) in, after the residue of aluminum-extracted pulverized fuel ash drying dehydration, its each component is counted in the form of an oxide, bag
Contain：The SiO of 41.0～56.0wt%2, 16.0～32.0wt% Al2O3, 2.0～3.9wt% TiO2, 0.4～0.9wt%
Fe2O3。
Normally, when addition inorganic filler prepares rubber in plastic substrate, due to inorganic filler and rubber matrix
Dispersibility in rubber matrix of the compatibility and inorganic filler it is poor, therefore obtained rubber poor-performing is crisp
Property big, poor toughness.And the present invention can make an addition to rubber by being modified the gum filler for obtaining to residue of aluminum-extracted pulverized fuel ash
Rubber is prepared in matrix, it is good with the compatibility of rubber matrix, the good dispersion in rubber matrix, the rubber for preparing
Also preferably, toughness strengthens glue product propertiess.
Technical scheme, realizes the twice laid of residue of aluminum-extracted pulverized fuel ash, while turning waste into wealth, it is to avoid
Residue of aluminum-extracted pulverized fuel ash is directly discharged to environment, also reduces the production cost of polypropylene plastics products, is improve
Economic benefit.
Preferably, the particle diameter of the fine-ground fly-ash residue of aluminum-extracted is d90≤ 3 μm, such as 2.5,2 or 1.5 μm, pH is 6-
7。
Preferably, the levigate time is 1.5～3h, to ensure that the particle diameter of fine-ground fly-ash residue of aluminum-extracted is in d90≤ 3 μm
In the range of.
The granularity of residue of aluminum-extracted pulverized fuel ash is less, and it is added into the rubber system that rubber matrix is prepared as inorganic filler
Moral character can be better.
Process of Surface Modification is known in the art, for example, directly mix to reach chemical cladding；Preferably, the step
(2) in, it is modified 15-30min at normal temperatures that the surface is modified.
Preferably, the preparation method is comprised the following steps：
(1) it is 6-7 residue of aluminum-extracted pulverized fuel ash to be placed in machine for cutting charge into pieces into filter-press water-washing to pH, and wet method is levigate obtains D90≤3
μm residue of aluminum-extracted pulverized fuel ash powder body；Preferably, the levigate time is 1.5～3h；
(2) water and surface is added to change in the residue of aluminum-extracted pulverized fuel ash powder body for obtaining step (1) according to ratio of weight and number
Property agent, at normal temperatures be modified 15-30min, obtain modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler.
Preferably, the consumption of the surface modifier is the 0.5-2.5wt% of the residue of aluminum-extracted pulverized fuel ash, preferred 1-
2wt%, such as 1.5wt%.
Preferably, the surface modifier is that weight ratio is 1:(0.5-2) stearic acid and Oleic acid, preferably weight ratio is
1:(0.8-1.5) stearic acid and Oleic acid, such as weight ratio is 1:1 stearic acid and Oleic acid.
Inventor it has been investigated that, when surface modifier be weight ratio be 1:(0.5-2) stearic acid and Oleic acid, especially
Weight ratio is 1:(0.8-1.5) stearic acid and Oleic acid, such as weight ratio is 1:When 1 stearic acid and Oleic acid, resulting rubber
Glue filler is good with the compatibility of rubber matrix, its good dispersion in rubber matrix, and the globality of obtained rubber
Can improve a lot.
Preferably, the surface modifier is that weight ratio is 1:(0.5-2):(0.2-1) stearic acid, Oleic acid and Oleic acid
Sodium, preferably weight ratio is 1:(0.5-1.6):(0.4-0.8) stearic acid, Oleic acid and enuatrol, such as weight ratio are 1:
0.5:0.5 stearic acid, Oleic acid and enuatrol.
Inventor it has been investigated that, when surface modifier be weight ratio be 1:(0.5-2):(0.2-1) stearic acid, oil
Acid and enuatrol, especially weight ratio are 1:(0.5-1.6):(0.4-0.8) stearic acid, Oleic acid and enuatrol, such as weight
Than for 1:0.5:When 0.5 stearic acid, Oleic acid and enuatrol, the compatibility of resulting gum filler and rubber matrix more preferably,
Its dispersibility in rubber matrix is more preferable, and the overall performance of obtained rubber is greatly improved.
Other side for achieving the above object, the present invention also provides a kind of prepared using above-mentioned preparation method
Gum filler.
Another aspect for achieving the above object, present invention also offers a kind of compounded rubber, the compound rubber
Glue includes rubber and using gum filler obtained in above-mentioned preparation method；Preferably, in mass, the rubber is filled out with rubber
The amount ratio of material is 10:4-6, such as 10:5.
The beneficial effects of the present invention is：
The gum filler of the present invention, by being modified to residue of aluminum-extracted pulverized fuel ash with surface modifier, improves it with modeling
The compatibility of material matrix, can not only turn waste into wealth, it is to avoid residue of aluminum-extracted pulverized fuel ash is directly discharged to environment, while
The cost of rubber on the basis of the performance for not reducing rubber, can also be reduced, is increased economic efficiency.
Specific embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following examples are only used
In explanation present disclosure, protection scope of the present invention is not limited to.The present invention is carried out using the design of the present invention
Simple change all in the scope of protection of present invention.
In following examples, model BR-9000 of butadiene rubber used, producer is the limited public affairs of Sinopec's share
Department's Shanghai Gaoqiao Petrochemical Company；
Model SBR-1500 of butadiene-styrene rubber, producer is PetroChina Company Ltd.'s Jilin Petrochemical point public affairs
Department；
Model X (S) K-160 of opening rubber mixing machine, producer is the first rubber and plastics machine of Wuxi City factory；
Model 0.63MN of vulcanizing press, producer be mighty force rubber and plastics machine company limited of Shanghai Sigma, conditions of vulcanization
For：150 DEG C of curing temperature, sulfide stress 15MPa, cure time 10min；
The method of testing of each parameter is as follows in table 2：300% stretching strength of vulcanization of rubber glue, tensile strength, extension at break
Rate is tested according to GB/T528-2009, and hardness is tested according to GB/T531.1-2008.
The preparing raw material of residue of aluminum-extracted pulverized fuel ash
The preparing raw material of residue of aluminum-extracted pulverized fuel ash is the recirculating fluidized bed coal powder of certain steam power plant's output, and its chemical composition is such as
Shown in table 1.
The circulating fluid bed coal ash chemical composition (wt%) of table 1
| SiO2 | Al2O3 | TiO2 | CaO | MgO | Fe2O3 | FeO | K2O | Na2O | LOS | SO2 | Summation |
| 34.70 | 46.28 | 1.48 | 3.61 | 0.21 | 1.54 | 0.22 | 0.39 | 0.17 | 7.17 | 1.32 | 95.77 |
Embodiment 1
Above-mentioned fluidization bed fly ash (table 1) is taken, 200 mesh (Taylor standard sieve) are crushed to, is added water and is made solid content and be
The slurry of 33wt%, (referring to Chinese patent CN102145905A, and entire contents is incorporated herein) using vertical-ring magnetic separator,
Twice of the magnetic separation in the case where field intensity is 1.5 ten thousand GS, the filter cake that solid content is 37.5wt% is obtained Jing after filter press filter pressing；To described
Concentration is added to carry out sour molten reaction, the HCl in hydrochloric acid and the aluminium oxide in flyash for the technical hydrochloric acid of 28wt% in filter cake
Mol ratio is 6:1,150 DEG C of reaction temperature, reaction pressure 0.6MPa, response time 2h, product Jing pressure filter (Hubei Xiangyang
In grind fine straining environmental protection equipment company limited XMY2-450 types) (pressure is 18MPa to solid-liquid separation, pressurising time 3min, time of filter pressing
5min), flyash acid dissolution slag G1 is obtained, its water content is determined to 47.5wt%.
It is 6-7 to take above-mentioned flyash acid dissolution slag G1 filter-press water-washing to pH value, is filtered, in being placed in 80 DEG C of air dry oven,
Drying is not more than 0.1wt% to water content, obtains desciccate (residue of aluminum-extracted pulverized fuel ash) G2.
The gum filler of embodiment 2
Raw material：1.5g sodium stearates, G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 2 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter sodium stearate, be modified at normal temperatures 30min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y1.
The rubber of embodiment 2 '
Raw material：100g butadiene rubbers, 2.0g stearic acid, 4.0g Zinc Oxide, 0.5g captaxs, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulfur, gum filler Y1 obtained in 50g embodiments 2；
Preparation method：
Butadiene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z1 is obtained.
The gum filler of embodiment 3
Raw material：1g Oleic acid is received, G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 2.5 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter Oleic acid to receive, be modified at normal temperatures 15min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y2.
The rubber of embodiment 3 '
Raw material：100g butadiene rubbers, 2.0g stearic acid, 4.0g Zinc Oxide, 0.5g captaxs, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulfur, gum filler Y2 obtained in 50g embodiments 3；
Preparation method：
Butadiene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z2 is obtained.
The gum filler of embodiment 4
Raw material：1g Oleic acid, G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 1.5 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter Oleic acid, be modified at normal temperatures 15min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y3.
The rubber of embodiment 4 '
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, gum filler Y3 obtained in 50g embodiments 4；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z3 is obtained.
The gum filler of embodiment 5
Raw material：2g stearic acid, G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 1.5 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter stearic acid, be modified at normal temperatures 30min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y4.
The rubber of embodiment 5 '
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, gum filler Y4 obtained in 50g embodiments 5；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z4 is obtained.
The gum filler of embodiment 6
Raw material：1g stearic acid, 1g Oleic acid, G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 1.7 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter stearic acid and Oleic acid, be modified at normal temperatures 30min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y5.
The rubber of embodiment 6 '
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, gum filler Y5 obtained in 50g embodiments 6；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z5 is obtained.
The gum filler of embodiment 7
Raw material：1g stearic acid, 0.5g Oleic acid, 0.5g enuatrols, (aluminum-extracted pulverized fuel ash is residual for G2 obtained in 100g embodiments 6
Slag)；
Preparation method：
(1) it is 1.8 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, obtains fine-ground fly-ash residue of aluminum-extracted；
(2) it is 1 according to solid-to-liquid ratio:1.5 add water in the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and add
Enter stearic acid, Oleic acid and enuatrol, be modified at normal temperatures 30min, obtains modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler Y6.
The rubber of embodiment 7 '
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, gum filler Y6 obtained in 50g embodiments 7；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z6 is obtained.
The rubber of embodiment 8 '
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, gum filler Y6 obtained in 25g embodiments 7,25g charcoals
It is black；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z7 is obtained.
The gum filler of comparative example 1
Raw material：G2 (residue of aluminum-extracted pulverized fuel ash) obtained in 100g embodiments 1；
Preparation method：
(1) it is 2 μm to granularity D90 G2 to be placed in into wet method in machine for cutting charge into pieces levigate, and the fine-ground fly-ash for obtaining D90≤2 μm is carried
Residue of aluminum；
(2) the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1) is dried, breaks up, and obtains gum filler Y7.
The rubber of comparative example 1 '
Raw material：100g butadiene rubbers, 2.0g stearic acid, 4.0g Zinc Oxide, 0.5g captaxs, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulfur, gum filler Y7 obtained in 50g comparative examples 1；
Preparation method：
Butadiene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z8 is obtained.
The rubber of comparative example 2 '
Raw material：100g butadiene-styrene rubber, 2.0g stearic acid, 4.0g Zinc Oxide, 0.5g captaxs, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulfur, gum filler Y7 obtained in 50g comparative examples 1；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z9 is obtained.
The rubber of comparative example 3
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, 50g white carbon blacks；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z10 is obtained.
The rubber of comparative example 4
Raw material：100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g Zinc Oxide, 1.0g captaxs, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulfur, the work that embodiment 1 is obtained in the B of 50gCN 102775816
Property modified lime-ash Y8；
Preparation method：
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after kneading on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes under 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z11 is obtained.
Above example 2 ' -8 ' and comparative example 1 ', the performance test results of obtained vulcanizate are shown in Table 2 in 2 ', 3,4.
The performance test results of the vulcanizate of table 2
According to table 2, from the comparison of embodiment 2 ' -7 ' and comparative example 1 ' and 2 ', surface-modified aluminum-extracted pulverized fuel ash
Residue adds the vulcanizate prepared in rubber matrix, and elongation at break and firmness change are little, but its 300% stress at definite elongation,
Tensile strength is significantly improved, and shows that modified residue of aluminum-extracted pulverized fuel ash can significantly improve the combination property of rubber.
From embodiment 2 ', 3 ' and comparative example 1 ', surface-modified residue of aluminum-extracted pulverized fuel ash is added in butadiene rubber
The vulcanizate of preparation, its 300% stress at definite elongation, tensile strength are improved, and elongation at break and firmness change are little, and firmly
Modified effect of the modified effect of fat acid sodium better than enuatrol.The modified residue of aluminum-extracted pulverized fuel ash vulcanizate 300% of sodium stearate
Stress at definite elongation, tensile strength have been respectively increased 30.8%, 28.8% than unmodified residue of aluminum-extracted pulverized fuel ash vulcanizate respectively.Table
Bright modified residue of aluminum-extracted pulverized fuel ash can significantly improve the combination property of butadiene rubber.
From embodiment 4 ' -7 ' and comparative example 2 ', surface-modified residue of aluminum-extracted pulverized fuel ash is added in butadiene-styrene rubber
The vulcanizate of preparation, its 300% stress at definite elongation, tensile strength are improved, and elongation at break and firmness change less, show
Modified residue of aluminum-extracted pulverized fuel ash can improve the combination property of butadiene-styrene rubber.Comparing embodiment 7 ' and comparative example 2 ' understand, change
300% stress at definite elongation of the residue of aluminum-extracted pulverized fuel ash vulcanizate of property, tensile strength vulcanize than unmodified residue of aluminum-extracted pulverized fuel ash
Glue has been respectively increased 40.7%, 32.8%.
Comparing embodiment 4 ' and embodiment 5 ', with the butadiene-styrene rubber sulfur that stearic acid modified residue of aluminum-extracted pulverized fuel ash is filler
Change 300% stress at definite elongation, the tensile strength of glue higher than the residue of aluminum-extracted pulverized fuel ash butylbenzene vulcanizate that Oleic acid is modified, show stearic acid
Modified effect better than Oleic acid modified effect.
From the comparison of embodiment 5 ' and 6 ', in the case where other conditions are the same, when surface modifier is weight ratio
For 1:The sulfuration obtained when the vulcanizate obtained when 1 stearic acid and Oleic acid relative to surface modifier is single stearic acid
Glue, 300% stress at definite elongation, tensile strength have increased slightly, and less, its combination property is carried for elongation at break and firmness change
It is high.
From the comparison of embodiment 6 ' and 7 ', in the case where other conditions are the same, when surface modifier is weight ratio
For 1:0.5:The vulcanizate obtained when 0.5 stearic acid, Oleic acid and enuatrol, relative to surface modifier be weight ratio be 1:1
Stearic acid and the vulcanizate that obtains during Oleic acid, its 300% stress at definite elongation improves, and tensile strength, elongation at break and hardness become
Change less, combination property is improved.
From the comparison of embodiment 7 ' and 8 ', in the case where other conditions are the same, with 50% white carbon black 50% is substituted
Residue of aluminum-extracted pulverized fuel ash, its 300% stress at definite elongation improves, and tensile strength is significantly improved, and elongation at break and firmness change are not
Greatly, combination property is improved significantly.
From embodiment 8 ' and comparative example 3, the white carbon black that residue of aluminum-extracted pulverized fuel ash substitutes 50% is added in rubber matrix
Obtained vulcanizate, relative to making vulcanizate obtained in filler with white carbon black completely, its combination property quite, and the price of white carbon black with
Residue of aluminum-extracted pulverized fuel ash is compared, it is expensive a lot.The method of the present invention, reduces cost, has saved resource, improves coal ash lifting
The comprehensive utilization value of residue of aluminum.
From the comparison of embodiment 5 ' and comparative example 4, in the case where other conditions are the same, when with CN 102775816
The active modification lime-ash that embodiment 1 is obtained in B is added when preparing vulcanizate in rubber matrix as inorganic filler, obtained sulfuration
Far below the combination property of the vulcanizate for preparing the filler of the present invention, this is absolutely proved the combination property of glue, the present invention
, used as the inorganic filler of rubber matrix, obtained cured properties is good, and can also reduce sulfur for modified residue of aluminum-extracted pulverized fuel ash
Change the production cost of glue, kill two birds with one stone, huge is affected on the industrial efficiency of rubber.
Claims (10)
1. a kind of preparation method of gum filler, it is characterised in that the preparation method is comprised the following steps：
(1) residue of aluminum-extracted pulverized fuel ash is washed and wet method is levigate, obtain fine-ground fly-ash residue of aluminum-extracted；
(2) add water and surface modifier to carry out surface in the fine-ground fly-ash residue of aluminum-extracted obtained to step (1) to be modified, obtain
Modified coal ash residue of aluminum-extracted；
(3) the modified coal ash residue of aluminum-extracted for obtaining step (2) is dried, breaks up, and obtains gum filler；
Wherein, the surface modifier is the combination of any one or more in stearic acid, sodium stearate, Oleic acid and enuatrol.
2. preparation method according to claim 1, it is characterised in that in the step (1), the fine-ground fly-ash carries aluminum
The particle diameter of residue is d90≤ 3 μm, pH is 6-7；Preferably, the levigate time is 1.5～3h.
3. preparation method according to claim 1 and 2, it is characterised in that the consumption of the surface modifier is the powder
The 0.5-2.5wt% of coal ash residue of aluminum-extracted.
4. preparation method according to claim 3, it is characterised in that it is 1 that the surface modifier is weight ratio:(0.5-
2) stearic acid and Oleic acid.
5. preparation method according to claim 4, it is characterised in that it is 1 that the surface modifier is weight ratio:(0.8-
1.5) stearic acid and Oleic acid.
6. preparation method according to claim 3, it is characterised in that it is 1 that the surface modifier is weight ratio:(0.5-
2):(0.2-1) stearic acid, Oleic acid and enuatrol.
7. preparation method according to claim 6, it is characterised in that it is 1 that the surface modifier is weight ratio:(0.5-
1.6):(0.4-0.8) stearic acid, Oleic acid and enuatrol.
8. the preparation method according to any one of claim 1,2 or 4-7, it is characterised in that in the step (2), institute
It is modified 15-30min at normal temperatures to state surface modified.
9. gum filler obtained in a kind of preparation method using as described in any one of claim 1-8.
10. a kind of compounded rubber, the compounded rubber includes rubber and gum filler as claimed in claim 9；Preferably, with
Quality meter, the rubber is 10 with the amount ratio of gum filler:(4-6).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110643074A (en) * | 2019-11-04 | 2020-01-03 | 安徽工业大学 | Reinforcing, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler and preparation method thereof |
| CN112916200A (en) * | 2019-12-05 | 2021-06-08 | 山西奇色环保科技有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN114507456A (en) * | 2022-01-20 | 2022-05-17 | 葫芦岛市健坤龙联高分子新型材料有限公司 | Method for preparing modified rubber filler by using electrode residual block |
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| CN1313354A (en) * | 2001-04-06 | 2001-09-19 | 高象升 | Process for preparing rubber-strengthening agent from powdered coal ash |
| CN101020765A (en) * | 2007-03-16 | 2007-08-22 | 中国地质大学（武汉） | Process of preparing natural rubber filler with solid waste oil shale |
| CN102775816A (en) * | 2012-08-14 | 2012-11-14 | 吉林大学 | Method for preparing rubber filler by modifying coal ash waste slag obtained after extracting aluminum through acid process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313354A (en) * | 2001-04-06 | 2001-09-19 | 高象升 | Process for preparing rubber-strengthening agent from powdered coal ash |
| CN101020765A (en) * | 2007-03-16 | 2007-08-22 | 中国地质大学（武汉） | Process of preparing natural rubber filler with solid waste oil shale |
| CN102775816A (en) * | 2012-08-14 | 2012-11-14 | 吉林大学 | Method for preparing rubber filler by modifying coal ash waste slag obtained after extracting aluminum through acid process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643074A (en) * | 2019-11-04 | 2020-01-03 | 安徽工业大学 | Reinforcing, flame-retardant and wear-resistant all-industrial solid waste type composite rubber filler and preparation method thereof |
| CN112916200A (en) * | 2019-12-05 | 2021-06-08 | 山西奇色环保科技有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN112916200B (en) * | 2019-12-05 | 2022-06-17 | 山西奇色环保科技股份有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN114507456A (en) * | 2022-01-20 | 2022-05-17 | 葫芦岛市健坤龙联高分子新型材料有限公司 | Method for preparing modified rubber filler by using electrode residual block |
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