CN106590066B - A kind of preparation method of gum filler, gum filler and compounded rubber - Google Patents
A kind of preparation method of gum filler, gum filler and compounded rubber Download PDFInfo
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- CN106590066B CN106590066B CN201610983064.7A CN201610983064A CN106590066B CN 106590066 B CN106590066 B CN 106590066B CN 201610983064 A CN201610983064 A CN 201610983064A CN 106590066 B CN106590066 B CN 106590066B
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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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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The present invention discloses preparation method and the gum filler of a kind of gum filler, including:(1) residue of aluminum-extracted pulverized fuel ash is washed, wet method is levigate, obtains fine-ground fly-ash residue of aluminum-extracted;(2) water is added into fine-ground fly-ash residue of aluminum-extracted and surface modifier carries out surface modification, obtains modified coal ash residue of aluminum-extracted;(3) modified coal ash residue of aluminum-extracted is dry, break up, obtain gum filler;Wherein, surface modifier is stearic acid, odium stearate, oleic acid and enuatrol any one or more of;The invention also discloses the compounded rubbers being prepared by the filler.The preparation method of the present invention is simple, by being modified to residue of aluminum-extracted pulverized fuel ash with surface modifier, improve its compatibility with plastic substrate, it can not only turn waste into wealth, residue of aluminum-extracted pulverized fuel ash direct emission is avoided to pollute the environment, gum filler obtained can be added largely, on the basis of not reducing the performance of rubber product, the cost for reducing rubber product, increases economic efficiency.
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 generate industrial solid castoff, be the larger industrial residue of the current discharge capacity in 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 both causes soil
The environmental pollutions such as ground, water body and air and ecological environment destruction, and the precious resources as silicate material is wasted, it is badly in need of out
High value added product is sent out, is efficiently utilized, to promote China's economizing type recycling economy development.If to total utilization of PCA
Research and processing are not gone into overdrive, it will bring immeasurable consequence to production of energy, comprehensive utilization of resources and environmental protection.
The composition of various regions flyash is different, for Al2O3The high flyash of content generally uses acid system or alkaline process by aluminium from flyash
It extracts, makes full use of regenerated resources, improve the comprehensive utilization value of flyash.Residue of aluminum-extracted pulverized fuel ash has particle thin
The high feature of small, short texture, activity, using with apparent technical advantage and economic advantages in high molecular material.At present
In terms of the utilization of residue of aluminum-extracted pulverized fuel ash is concentrated mainly on construction material, 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 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 superfine powder》.This method is with discarded powder
Coal ash is raw material, is carried out at cladding and chemical modification, coupling with nano-calcium carbonate by ultra-fine grinding, activation, then to its surface
Reason, obtains that the coveredwith nanometer calcium carbonate flyash superfine powder that precipitated calcium carbonate is filled in rubber and plastic products can be substituted.
Preferably 32 μm of the fineness of pulverized-coal ash of ultra-fine grinding, residue on sieve≤8wt% in the patent;Modified-reaction temperature is 70 DEG C~90 DEG C,
The flyash superfine powder product granularity that the method obtains is thicker, and technique is more complex.102775816 A of CN are disclosed《Acid system carries
Flyash waste after aluminium is modified the method for preparing gum filler》.This method acid system is carried the flyash waste after aluminium elute to
It is dry, pulverize after neutrality to 300 mesh, organic modifiers is added, mixed at high speed, grinding are gum filler after ageing.The method
Although the cost of rubber product can be reduced, and solid waste coal ash residue of aluminum-extracted can be effectively utilized, reduce ecological ring
The pollution in border, but obtained gum filler granularity is larger, only reaches 300 mesh, and good strengthening action cannot be played to rubber.
Invention content
The purpose of the present invention is to provide a kind of preparation method of gum filler and gum filler, which is to utilize
Residue of aluminum-extracted pulverized fuel ash is prepared, and has good compatibility, the good dispersion in rubber matrix with rubber matrix.
It is another object of the present invention to provide a kind of compounded rubber, the compounded rubber performance is good.
The one side of purpose to realize the present invention, the present invention provides a kind of preparation method of gum filler, use
Technical solution is as follows:
A kind of preparation method of gum filler, includes 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) water is added in the fine-ground fly-ash residue of aluminum-extracted obtained to step (1) and surface modifier carries out surface modification,
Obtain modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler;
Wherein, the surface modifier be stearic acid, odium stearate, oleic acid and enuatrol any one or more of group
It closes.
In the present invention, the residue of aluminum-extracted pulverized fuel ash refers to the residue of formation after flyash extraction aluminium oxide.Powder
Coal ash residue of aluminum-extracted is it is known in the art, can obtain by conventional method.For example, can by CN102153117A,
The methods of CN101870489A, CN102145904A, CN102145905A obtain residue of aluminum-extracted pulverized fuel ash.Such as
Acid is molten disclosed in CN102145905A puies forward aluminium technique, it is incorporated into the application by reference.Specifically, 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 through crush reach 100 mesh hereinafter, plus water be made into solid content be 20~
The slurry of 40wt%, carries out magnetic separation on vertical ring magnetic separator, the GS of magnetic separation field strength 1.0~2.0 ten thousand;Slurry after magnetic separation is through solid-liquid
The filter cake that solid content is 25~50wt% is obtained after separation;
2), acid is molten:By the filter cake after magnetic separation be placed in acid-resistant reacting kettle carry out hydrochloric acid acid it is molten, concentration of hydrochloric acid be 20~
35wt%, the molar ratio of HCl and aluminium oxide in flyash is 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 is 20~30wt%, in hydrochloric acid HCl with
The molar 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 are 1.5h~2.5h;Product obtains the residue of aluminum-extracted pulverized fuel ash through being separated by solid-liquid separation after acid is molten.
Above-mentioned steps 2) in, the residue of aluminum-extracted pulverized fuel ash after drying and dehydrating, count in the form of an oxide by each component, packet
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 into plastic substrate, addition inorganic filler prepares rubber product, due to inorganic filler and rubber matrix
Dispersibility in rubber matrix of compatibility and inorganic filler it is poor, therefore rubber product performance obtained is poor, crisp
Big, the poor toughness of property.And the present invention can make an addition to rubber by the gum filler being modified to residue of aluminum-extracted pulverized fuel ash
Rubber product is prepared in matrix, good dispersion in rubber matrix good with the compatibility of rubber matrix, the rubber being prepared
Glue product properties is also preferable, toughness enhancing.
Technical scheme of the present invention realizes the waste utilization of residue of aluminum-extracted pulverized fuel ash, while turning waste into wealth, avoids
Residue of aluminum-extracted pulverized fuel ash direct emission pollutes the environment, and also reduces the production cost of polypropylene plastics products, improves
Economic benefit.
Preferably, the grain size of the fine-ground fly-ash residue of aluminum-extracted is d90≤ 3 μm, such as 2.5,2 or 1.5 μm, pH 6-
7。
Preferably, the levigate time is 1.5~3h, to ensure that the grain size of fine-ground fly-ash residue of aluminum-extracted is in d90≤ 3 μm
In range.
The granularity of residue of aluminum-extracted pulverized fuel ash is smaller, and the rubber system that rubber matrix is prepared is added into as inorganic filler
Moral character can be better.
Process of Surface Modification is known in the art, such as directly mixing is to reach chemical cladding;Preferably, the step
(2) in, it is modified 15-30min at normal temperatures that the surface, which is modified,.
Preferably, the preparation method comprises 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 filter-press water-washing to pH, and wet method is levigate obtains D90≤3
μm residue of aluminum-extracted pulverized fuel ash powder;Preferably, the levigate time is 1.5~3h;
(2) water is added into the residue of aluminum-extracted pulverized fuel ash powder for obtaining step (1) according to weight part ratio and surface changes
Property agent, at normal temperatures be modified 15-30min, obtain modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler.
Preferably, the dosage of the surface modifier is the 0.5-2.5wt%, preferably 1- of the residue of aluminum-extracted pulverized fuel ash
2wt%, such as 1.5wt%.
Preferably, it is 1 that the surface modifier, which is weight ratio,:The stearic acid and oleic acid of (0.5-2), preferably weight ratio are
1:The stearic acid and oleic acid of (0.8-1.5), such as weight ratio are 1:1 stearic acid and oleic acid.
Inventor it has been investigated that, be 1 when surface modifier is weight ratio:The stearic acid and oleic acid of (0.5-2), especially
Weight ratio is 1:The stearic acid and oleic acid of (0.8-1.5), such as weight ratio are 1:When 1 stearic acid and oleic acid, obtained rubber
The compatibility of glue filler and rubber matrix is good, the good dispersion in rubber matrix, prepared by rubber product globality
It can improve a lot.
Preferably, it is 1 that the surface modifier, which is weight ratio,:(0.5-2):Stearic acid, oleic acid and the oleic acid of (0.2-1)
Sodium, preferably weight ratio are 1:(0.5-1.6):Stearic acid, oleic acid and the enuatrol of (0.4-0.8), such as weight ratio are 1:
0.5:0.5 stearic acid, oleic acid and enuatrol.
Inventor it has been investigated that, be 1 when surface modifier is weight ratio:(0.5-2):(0.2-1), stearic acid, oil
Acid and enuatrol, especially weight ratio are 1:(0.5-1.6):Stearic acid, oleic acid and the enuatrol of (0.4-0.8), such as weight
Than being 1:0.5:When 0.5 stearic acid, oleic acid and enuatrol, the compatibility of obtained gum filler and rubber matrix is more preferable,
Its dispersibility in rubber matrix is more preferable, prepared by rubber product overall performance be greatly improved.
Other side for achieving the above object is made the present invention also provides a kind of using above-mentioned preparation method
Gum filler.
Another aspect for achieving the above object, the present invention also provides a kind of compounded rubber, the compound rubber
Glue includes gum filler made from rubber and the above-mentioned preparation method of utilization;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 are:
The gum filler of the present invention improves itself and modeling by being modified to residue of aluminum-extracted pulverized fuel ash with surface modifier
The compatibility for expecting matrix, can not only turn waste into wealth, avoid residue of aluminum-extracted pulverized fuel ash direct emission from polluting the environment, simultaneously
It can also reduce the cost of rubber product on the basis of not reducing the performance of rubber product, increase economic efficiency.
Specific implementation mode
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following embodiment is only used
In illustrating present disclosure, the protection domain that is not intended to restrict the invention.The present invention is carried out using the design of the present invention
It is simple change all in the scope of protection of present invention.
In following embodiment, the model BR-9000 of butadiene rubber used, producer is the limited public affairs of Sinopec's share
Take charge of Shanghai Gaoqiao Petrochemical Company;
The model SBR-1500 of butadiene-styrene rubber, producer are PetroChina Company Ltd.'s Jilin Petrochemical point public affairs
Department;
Model X (S) K-160 of opening rubber mixing machine, producer are the first rubber and plastics machine of Wuxi City factory;
The model 0.63MN of vulcanizing press, producer are mighty force rubber and plastics machine Co., Ltd of Shanghai Sigma, conditions of vulcanization
For:150 DEG C, sulfide stress 15MPa, vulcanization time 10min of curing temperature;
The test method 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.
Residue of aluminum-extracted pulverized fuel ash prepares raw material
Residue of aluminum-extracted pulverized fuel ash prepares the recirculating fluidized bed coal powder that raw material is certain steam power plant's output, and chemical composition is such as
Shown in table 1.
1 circulating fluid bed coal ash chemical composition (wt%) of table
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, adds water that solid content is made to be
The slurry of 33wt% (is incorporated herein) using vertical-ring magnetic separator referring to Chinese patent CN102145905A, and by entire contents,
In the case where field strength is 1.5 ten thousand GS, twice of magnetic separation, obtains the filter cake that solid content is 37.5wt% after plate and frame filter press press filtration;To described
The technical hydrochloric acid that a concentration of 28wt% is added in filter cake carries out the molten reaction of acid, the aluminium oxide in HCl and flyash in hydrochloric acid
Molar ratio is 6:1,150 DEG C, reaction pressure 0.6MPa, reaction time 2h of reaction temperature, reaction product is through filter press (Hubei Xiangyang
In grind refined filtration environmental protection equipment Co., Ltd XMY2-450 types) be separated by solid-liquid separation (pressure 18MPa, pressurising time 3min, time of filter pressing
5min), flyash acid dissolution slag G1 is obtained, water content is determined to 47.5wt%.
It is 6-7 to take above-mentioned flyash acid dissolution slag G1 filter-press water-washings to pH value, and filtering is placed in 80 DEG C of air dry oven,
It is dry to be not more than 0.1wt% to water content, obtain desciccate (residue of aluminum-extracted pulverized fuel ash) G2.
2 gum filler of embodiment
Raw material:1.5g odium stearate, G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 2 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter odium stearate, is modified 30min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y1.
2 ' rubber product of embodiment
Raw material:100g butadiene rubbers, 2.0g stearic acid, 4.0g zinc oxide, 0.5g captaxes, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulphur, gum filler Y1 made from 50g embodiments 2;
Preparation method:
Butadiene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z1 is made.
3 gum filler of embodiment
Raw material:1g oleic acid is received, G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 2.5 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter oleic acid to receive, is modified 15min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y2.
3 ' rubber product of embodiment
Raw material:100g butadiene rubbers, 2.0g stearic acid, 4.0g zinc oxide, 0.5g captaxes, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulphur, gum filler Y2 made from 50g embodiments 3;
Preparation method:
Butadiene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z2 is made.
4 gum filler of embodiment
Raw material:1g oleic acid, G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 1.5 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter oleic acid, is modified 15min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y3.
4 ' rubber product of embodiment
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, gum filler Y3 made from 50g embodiments 4;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z3 is made.
5 gum filler of embodiment
Raw material:2g stearic acid, G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 1.5 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter stearic acid, is modified 30min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y4.
5 ' rubber product of embodiment
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, gum filler Y4 made from 50g embodiments 5;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z4 is made.
6 gum filler of embodiment
Raw material:1g stearic acid, 1g oleic acid, G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 1.7 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter stearic acid and oleic acid, is modified 30min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y5.
6 ' rubber product of embodiment
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, gum filler Y5 made from 50g embodiments 6;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z5 is made.
7 gum filler of embodiment
Raw material:1g stearic acid, 0.5g oleic acid, 0.5g enuatrols, (aluminum-extracted pulverized fuel ash is residual by G2 made from 100g embodiments 6
Slag);
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 1.8 μm, obtain fine-ground fly-ash residue of aluminum-extracted;
(2) it is 1 according to solid-to-liquid ratio:1.5 water is added into the fine-ground fly-ash residue of aluminum-extracted for obtaining step (1), and adds
Enter stearic acid, oleic acid and enuatrol, is modified 30min at normal temperatures, obtains modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y6.
7 ' rubber product of embodiment
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, gum filler Y6 made from 50g embodiments 7;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z6 is made.
8 ' rubber product of embodiment
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, gum filler Y6,25g charcoal made from 25g embodiments 7
It is black;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z7 is made.
1 gum filler of comparative example
Raw material:G2 (residue of aluminum-extracted pulverized fuel ash) made from 100g embodiments 1;
Preparation method:
(1) by G2 be placed in wet method in machine for cutting charge into pieces it is levigate to granularity D90 be 2 μm, the fine-ground fly-ash for obtaining D90≤2 μm carries
Residue of aluminum;
(2) by step (1) obtains, fine-ground fly-ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler Y7.
1 ' rubber product of comparative example
Raw material:100g butadiene rubbers, 2.0g stearic acid, 4.0g zinc oxide, 0.5g captaxes, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulphur, gum filler Y7 made from 50g comparative examples 1;
Preparation method:
Butadiene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z8 is made.
2 ' rubber product of comparative example
Raw material:100g butadiene-styrene rubber, 2.0g stearic acid, 4.0g zinc oxide, 0.5g captaxes, 1.0g accelerant CZs, 1.0g
Antioxidant 4010 A, 1.5g coumarone, 1.5g sulphur, gum filler Y7 made from 50g comparative examples 1;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z9 is made.
3 rubber product of comparative example
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, 50g carbon blacks;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z10 is made.
4 rubber product of comparative example
Raw material:100g butadiene-styrene rubber, 1.0g stearic acid, 5.0g zinc oxide, 1.0g captaxes, 1.5g accelerant CZs, 1.5g
Antioxidant 4010 A, 2.0g coumarone, 1.5g machinery oil, 1.5g sulphur, the work that embodiment 1 obtains in 102775816 B of 50gCN
Property be modified lime-ash Y8;
Preparation method:
Butadiene-styrene rubber is plasticated on opening rubber mixing machine, slice after being kneaded on opening rubber mixing machine by above-mentioned formula,
Then vulcanize 10 minutes at 150 DEG C of curing temperature, sulfide stress 15MPa, vulcanizate Z11 is made.
The performance test results of vulcanizate obtained are shown in Table 2 in above example 2 ' -8 ' and comparative example 1 ', 2 ', 3,4.
The performance test results of 2 vulcanizate of table
According to table 2, by the comparison of embodiment 2 ' -7 ' and comparative example 1 ' and 2 ' it is found that surface-modified aluminum-extracted pulverized fuel ash
The vulcanizate prepared in rubber matrix is added in residue, 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 comprehensive performance of rubber.
By embodiment 2 ', 3 ' and comparative example 1 ' it is found that surface-modified residue of aluminum-extracted pulverized fuel ash is added in butadiene rubber
The vulcanizate of preparation, 300% stress at definite elongation, tensile strength are improved, and elongation at break and firmness change are little, and hard
The modified effect of resin acid sodium is better than the modified effect of enuatrol.The residue of aluminum-extracted pulverized fuel ash vulcanizate 300% that odium stearate is modified
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 comprehensive performance of butadiene rubber.
By embodiment 4 ' -7 ' and comparative example 2 ' it is found that surface-modified residue of aluminum-extracted pulverized fuel ash is added in butadiene-styrene rubber
The vulcanizate of preparation, 300% stress at definite elongation, tensile strength are improved, and elongation at break and firmness change are little, show
The comprehensive performance of butadiene-styrene rubber can be improved in modified residue of aluminum-extracted pulverized fuel ash.Comparing embodiment 7 ' and comparative example 2 ' are it is found that 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 sulphur that stearic acid modified residue of aluminum-extracted pulverized fuel ash is filler
300% stress at definite elongation of change glue, tensile strength are higher than the residue of aluminum-extracted pulverized fuel ash butylbenzene vulcanizate that oleic acid is modified, and show stearic acid
Modified effect be better than oleic acid modified effect.
By embodiment 5 ' with 6 ' comparison it is found that in the case of as other conditions, when surface modifier is weight ratio
It is 1:The vulcanizate obtained when 1 stearic acid and oleic acid, the vulcanization relative to surface modifier to be obtained when single stearic acid
Glue, 300% stress at definite elongation, tensile strength have increased slightly, and elongation at break and firmness change are little, and comprehensive performance is carried
It is high.
By embodiment 6 ' with 7 ' comparison it is found that in the case of as other conditions, when surface modifier is weight ratio
It is 1:0.5:It is 1 that the vulcanizate obtained when 0.5 stearic acid, oleic acid and enuatrol, which relative to surface modifier is weight ratio,:1
Stearic acid and oleic acid when obtained vulcanizate, 300% stress at definite elongation improves, and tensile strength, elongation at break and hardness become
Change less, comprehensive performance is improved.
By embodiment 7 ' 50% is substituted with 50% carbon black with 8 ' comparison it is found that in the case of as other conditions
Residue of aluminum-extracted pulverized fuel ash, 300% stress at definite elongation improves, and tensile strength significantly improves, and elongation at break and firmness change are not
Greatly, comprehensive performance is improved significantly.
By embodiment 8 ' and comparative example 3 it is found that the carbon black of residue of aluminum-extracted pulverized fuel ash replacement 50% is added in rubber matrix
Vulcanizate obtained, relative to vulcanizate made from filler is made with carbon black completely, comprehensive performance is suitable, and the price of carbon black with
Residue of aluminum-extracted pulverized fuel ash is compared, it is expensive very much.The method of the present invention, reduces cost, has saved resource, improve coal ash lifting
The comprehensive utilization value of residue of aluminum.
By embodiment 5 ' with the comparison of comparative example 4 it is found that in the case of as other conditions, when with CN 102775816
When the active modification lime-ash that embodiment 1 obtains in B in inorganic filler addition rubber matrix as vulcanizate is prepared, vulcanization obtained
The comprehensive performance of glue is far below the comprehensive performance for the vulcanizate that the filler of the present invention is prepared, this is absolutely proved, the present invention
Inorganic filler of the modified residue of aluminum-extracted pulverized fuel ash as rubber matrix, cured properties obtained is good, and can also reduce sulphur
The production cost for changing glue, kills two birds with one stone, and is influenced on the industrial efficiency of rubber huge.
Claims (7)
1. a kind of preparation method of gum filler, which is characterized in that the preparation method 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) water is added in the fine-ground fly-ash residue of aluminum-extracted obtained to step (1) and surface modifier carries out surface modification, obtains
Modified coal ash residue of aluminum-extracted;
(3) by step (2) obtains, modified coal ash residue of aluminum-extracted is dry, breaks up, and obtains gum filler;
Wherein, it is 1 that the surface modifier, which is weight ratio,:(0.5-2):Stearic acid, oleic acid and the enuatrol of (0.2-1).
2. preparation method according to claim 1, which is characterized in that in the step (1), the fine-ground fly-ash carries aluminium
The grain size of residue is d90≤ 3 μm, pH 6-7;Preferably, the levigate time is 1.5~3h.
3. preparation method according to claim 1 or 2, which is characterized in that the dosage 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, which is characterized in that the surface modifier is that weight ratio is 1:(0.5-
1.6):Stearic acid, oleic acid and the enuatrol of (0.4-0.8).
5. according to the preparation method described in any one of claim 1,2 or 4, which is characterized in that described in the step (2)
It is modified 15-30min at normal temperatures that surface, which is modified,.
6. a kind of utilizing gum filler made from preparation method as described in any one in claim 1-5.
7. a kind of compounded rubber, the compounded rubber includes rubber and gum filler as claimed in claim 6;Preferably, with
The amount ratio of quality meter, the rubber and gum filler is 10:(4-6).
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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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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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