CN113913033B - Modified ball clay and preparation method thereof - Google Patents

Modified ball clay and preparation method thereof Download PDF

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CN113913033B
CN113913033B CN202111212438.2A CN202111212438A CN113913033B CN 113913033 B CN113913033 B CN 113913033B CN 202111212438 A CN202111212438 A CN 202111212438A CN 113913033 B CN113913033 B CN 113913033B
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ball clay
coupling agent
prepared
gamma
modified
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CN113913033A (en
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张武艺
易仕荣
张跃红
涂松柏
周勇
余国凤
贺大贵
冉茂刚
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Xiamen Xinyisheng New Material Technology Co ltd
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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
    • C09C1/42—Clays
    • 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
    • C08K3/346—Clay
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C09C3/06—Treatment with inorganic compounds
    • 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
    • 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
    • C09C3/12—Treatment with organosilicon compounds
    • 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
    • C01P2006/21—Attrition-index or crushing strength of granulates
    • 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

Abstract

The application relates to the field of preparation of ball clay, in particular to modified ball clay and a preparation method thereof, wherein the preparation method of the modified ball clay comprises the following steps: s1: drying the ball clay to obtain ball clay powder; s2: mixing ball clay powder with water to prepare a ball clay solution; s3: adding a coupling agent into the ball clay solution, and mixing and stirring to obtain a primary treatment material; the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of (3-5): (2-3); s4: and (5) performing suction filtration on the primary treatment material prepared in the step S3, and drying to obtain the catalyst. The preparation method has the advantage of improving the reinforcing effect of the prepared ball clay on rubber.

Description

Modified ball clay and preparation method thereof
Technical Field
The application relates to the field of preparation of ball clay, in particular to modified ball clay and a preparation method thereof.
Background
The ball clay is a clay mineral which takes microcrystalline kaolinite and alpha-quartz particles as main mineral components and has the advantages of rich resources, wide raw material sources, low price and the like; the ball clay has wide application as a filler, can be used as a filler for paper making, plastics, paints and organic polymers, and particularly can be used for reinforcing rubber by modifying the ball clay on the aspect of filling the rubber, and the modified ball clay can replace expensive white carbon black, so that a new idea is provided for the utilization of the ball clay; the ball clay is filled in the rubber to reinforce the property of the rubber by modifying the ball clay.
Disclosure of Invention
In order to improve the reinforcing effect of the prepared ball clay on rubber, the application provides a modified ball clay and a preparation method thereof.
The modified ball clay and the preparation method thereof adopt the following technical scheme:
a preparation method of modified ball clay comprises the following steps:
s1: crushing, sieving and drying the ball clay to obtain ball clay powder;
s2: mixing the ball clay powder prepared in the step S1 with water according to the mass ratio of 1: (2-3) preparing a ball clay solution;
s3: adding a coupling agent into the ball clay solution prepared in the step S2, and mixing to obtain a primary treatment material; the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of (3-5): (2-3);
s4: and (5) performing suction filtration on the primary treated material prepared in the step (S3), and drying to obtain the product.
By adopting the technical scheme, at least one of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate are compounded to form the coupling agent; because the gamma-glycidoxypropyltrimethoxysilane and the gamma-methacryloxypropyltrimethoxysilane are silane coupling agents, the silane coupling agents can be connected with the ball clay through the action of chemical bonding to modify the ball clay, the modified clay is not easy to agglomerate, and the modified ball clay is filled in rubber and has better dispersion performance; meanwhile, after gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane are hydrolyzed, one end of the hydrolyzed gamma-glycidoxypropyltrimethoxysilane and one end of the hydrolyzed gamma-methacryloxypropyltrimethoxysilane can form Si-O-Si chemical bonds with the surface of the ball clay, and active functional groups generated at the other end of the hydrolyzed gamma-glycidoxypropyltrimethoxysilane and the surface of the ball clay can generate crosslinking reaction with rubber, so that a stable bonding layer is formed and the rubber is reinforced; isopropyl tri (dioctyl pyrophosphato acyloxy) titanate is used as a titanate coupling agent, can also be connected with ball clay in a chemical bonding mode to modify the ball clay, and the ball clay modified by isopropyl tri (dioctyl pyrophosphato acyloxy) titanate can improve the processability of rubber after being filled into the rubber; the ball clay is modified by the coupling agent compounded by at least one of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, so that the reinforcing effect on rubber after the ball clay is added into the rubber is improved, and the reinforced rubber has good processability.
Preferably, the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato) titanate according to the mass ratio of (2-3): (1-2): (2-3).
By adopting the technical scheme, the gamma-glycidoxypropyltrimethoxysilane improves the adhesive property of the ball clay and the rubber by carrying out surface modification on the ball clay, so that the reinforcing effect on the rubber is improved; after the surface modification is carried out on the ball clay by the gamma-methacryloxypropyltrimethoxysilane, the modified ball clay can be stably combined with rubber after being filled in the rubber, and meanwhile, the durability of the modified rubber is improved; the ball clay modified by isopropyl tri (dioctyl pyrophosphato acyloxy) titanate can be filled in rubber, so that the processability of the rubber can be improved; the ball clay is modified by the combined action of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, so that the rubber is filled by the modified ball clay, the rubber is better reinforced, and the subsequent use performance of the rubber is improved.
Preferably, the mass ratio of the coupling agent to the ball clay solution in the step S3 is (1-2): (200-300).
By adopting the technical scheme, the mass ratio of the coupling agent to the ball clay solution is adjusted, and then the mass ratio of the coupling agent to the ball clay powder in the ball clay solution is adjusted; when the dosage of the coupling agent is too large, the reaction center on the surface of the ball clay is completely occupied, and the excessive coupling agent can not react with the ball clay any more, but is combined with the active groups of the coupling agent occupying the surface of the ball clay mutually by Van der Waals force, so that the active groups on the surface of the ball clay are reduced, and the subsequent bonding force with rubber molecules is weakened, thereby reducing the reinforcing property; when the dosage of the coupling agent is too small, the modification effect on the ball clay is insufficient, and the subsequent reinforcing effect of the ball clay on the rubber is influenced.
Preferably, after the ball clay powder is prepared in step S1, before the ball clay powder is mixed with water, the method further includes the following steps: soaking the ball clay powder in acid solution, precipitating, separating, washing and drying.
By adopting the technical scheme, the ball clay contains the alumina which has acid reaction activity and is easy to react with acid liquor, and pores can be formed on the surface of the reacted ball clay, so that the surface area of the ball clay is increased, the contact area of the ball clay and the coupling agent during reaction is increased, the modification effect of the coupling agent on the ball clay is further improved, and the reinforcement effect of the modified ball clay on rubber is enhanced.
Preferably, the acid solution is hydrochloric acid.
Through adopting above-mentioned technical scheme, adopt hydrochloric acid to carry out the acidizing to ball clay for the more also more even of the quantity of the hole that forms on ball clay surface, other acidizing fluids of hydrochloric acid comparison simultaneously are difficult for forming the complex with aluminium ion, make the speed that ball clay surface hole generated not slowed down.
Preferably, before adding the coupling agent to the ball clay solution in step S3, the method further includes the following steps: and (3) carrying out ultrasonic treatment on the ball clay solution for 8-10 h.
By adopting the technical scheme, the ball clay solution is subjected to ultrasonic treatment, the dispersity and the adsorbability of the ball clay are improved, the reaction degree of the subsequent coupling agent and the ball clay is further improved, and the modification effect of the coupling agent on the ball clay is better.
Preferably, after the coupling agent is added to the ball clay solution in step S3, before mixing, the method further comprises the following steps: adding an initiator into the ball clay solution, wherein the initiator is prepared from ammonium persulfate and sodium bisulfite according to a mass ratio of (3-4): (1-2).
By adopting the technical scheme, the ammonium persulfate and the sodium bisulfite can both generate oxidation-reduction reaction to initiate active groups on the surface of the ball clay, so that the chemical bonding process between the coupling agent and the ball clay is smoother, and the modification rate of the coupling agent to the ball clay is further improved.
Preferably, the mass ratio of the initiator to the coupling agent is (2-3): (1-2).
By adopting the technical scheme, the mass ratio of the initiator to the coupling agent is limited, so that after the initiator initiates the active groups on the surface of the ball clay, the coupling agent can be combined with the ball clay more quickly, and the modification effect of the coupling agent on the ball clay is further improved.
In a second aspect, the present application provides a modified ball clay, which adopts the following technical scheme:
a modified ball clay is prepared by a preparation method of the modified ball clay.
By adopting the technical scheme, the ball clay is modified by bonding the coupling agent prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate with the ball clay; the addition of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane improves the reinforcing effect on rubber, and simultaneously improves the durability of the reinforced rubber; meanwhile, the ball clay is modified by isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, so that the subsequent processing performance of the rubber is improved while the rubber is reinforced; the modified ball clay has better reinforcing effect on rubber through the combined action of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
In summary, the present application has the following beneficial effects:
1. as the gamma-glycidoxypropyltrimethoxysilane, the gamma-methacryloxypropyltrimethoxysilane and the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate are adopted as the coupling agents to modify the ball clay, the reinforcing effect of the modified ball clay on rubber is improved.
2. Before the ball clay powder is combined with the coupling agent, the ball clay powder is firstly put into acid liquor for impregnation, and the acid liquor reacts with alumina in the ball clay, so that pores are formed on the surface of the ball clay, the reaction area of the ball clay and the coupling agent is increased, and the modification effect of the coupling agent on the ball clay is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In the preparation method of the modified ball clay, the aluminum content in the ball clay is 25%;
when the coupling agent consists of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphate) titanate, the coupling agent consists of the mass sum of the gamma-glycidoxypropyltrimethoxysilane and the gamma-methacryloxypropyltrimethoxysilane and the isopropyl tri (dioctyl pyrophosphate) titanate according to the mass ratio of (3-5): (2-3); further, the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphoryl) titanate according to the mass ratio of (2-3): (1-2): (2-3);
the CAS number of the gamma-glycidoxypropyltrimethoxysilane used is 2530-83-8;
the CAS number of the gamma-methacryloxypropyltrimethoxysilane used is 2530-85-0;
the CAS number of the used isopropyl tri (dioctyl pyrophosphato acyloxy) titanate is 67691-13-8;
the molar concentration of the used hydrochloric acid is 2 mol/L;
the initiator consists of ammonium persulfate and sodium bisulfite, and the CAS number of the used ammonium persulfate is 7727-54-0; the CAS number of the sodium bisulfite is 7631-90-5;
examples
Example 1
The preparation method of the modified ball clay adopts the following technical scheme:
s1: crushing ball clay, sieving to remove large particle impurities, and drying to obtain ball clay powder;
s2: putting the ball clay powder prepared in the step S1 and water into a stirring barrel with a stirring paddle, wherein the stirring speed of the stirring paddle is set to be 40r/min, and the stirring time is 20min, so as to prepare a ball clay solution; the mass ratio of the ball clay powder to water is 1: 3;
s3: adding a coupling agent into the ball clay solution prepared in the step S2, setting the stirring speed of the stirring slurry to be 30r/min, and mixing and stirring for 15min to obtain a primary treatment material; the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 1: 1, preparing a composition; the mass ratio of the coupling agent to the ball clay solution is 1: 300, respectively;
s4: and (5) performing suction filtration and drying on the primary treated material prepared in the step S3 to obtain the catalyst.
Example 2
The preparation method of the modified ball clay of this example is different from that of example 1 in that the coupling agent added in step S3 is prepared from gamma-glycidoxypropyltrimethoxysilane and isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 5: 2, the rest being the same as in example 1.
Example 3
The preparation method of the modified ball clay of this example is different from that of example 1 in that the coupling agent added in step S3 is prepared from gamma-glycidoxypropyltrimethoxysilane and isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 4: 2.5, the rest being the same as in example 1.
Example 4
The preparation method of the modified ball clay of this example is different from that of example 1 in that the coupling agent added in step S3 is prepared from gamma-methacryloxypropyltrimethoxysilane and isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 4: 2.5, the rest being the same as in example 1.
Example 5
The method for preparing the modified ball clay of this example is different from that of example 1 in that the coupling agent added in step S3 is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 2.5: 1.5: 2.5, the rest being the same as in example 1.
Example 6
The method for producing a modified ball clay of this example is different from example 5 in that, when the coupling agent is added to the ball clay solution in step S3, the mass ratio of the coupling agent to the ball clay solution is 1: 100, the rest being the same as in example 5.
Example 7
The method for preparing a modified ball clay of this example is different from example 5 in that, when the coupling agent is added to the ball clay solution in step S3, the mass ratio of the coupling agent to the ball clay solution is 1: 200, the rest is the same as in example 5.
Example 8
The method for producing a modified ball clay of this example is different from example 5 in that a coupling agent is added to the ball clay solution in step S3, and the mass ratio of the coupling agent to the ball clay solution is 1: 500, the rest is the same as in example 5.
Example 9
The preparation method of the modified ball clay adopts the following technical scheme:
s1: crushing ball clay, sieving to remove large particle impurities, and drying to obtain ball clay powder;
s2: immersing the ball clay powder prepared in the step S1 in acid liquor, uniformly stirring, standing for 7h at 90 ℃, then precipitating to remove liquid, and washing and drying the solid to obtain a standby material; the acid solution is sulfuric acid solution with the molar concentration of 2 mol/L;
s3: putting the spare material prepared in the step S2 and water into a stirring barrel with a stirring paddle, wherein the stirring speed of the stirring paddle is set to be 40r/min, and the stirring time is 20min, so as to prepare a ball clay solution; the mass ratio of the standby materials to water is 1: 3;
s4: adding a coupling agent into the ball clay solution prepared in the step S3, setting the stirring speed of the stirring slurry to be 30r/min, and mixing and stirring for 15min to obtain a primary treatment material; the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphoryl) titanate according to the mass ratio of 2.5: 1.5: 2.5; the mass ratio of the coupling agent to the ball clay solution is 1: 200 of a carrier;
s5: and (5) performing suction filtration and drying on the primary treated material prepared in the step S4 to obtain the catalyst.
Example 10
The modified ball clay of this example was prepared in the same manner as in example 9 except that the acid solution used in step S2 was oxalic acid having a molar concentration of 2 mol/L.
Example 11
The process for producing a modified ball clay of this example was different from that of example 9 in that the acid solution used in step S2 was hydrochloric acid having a molar concentration of 2mol/L, and the rest was the same as that of example 9.
Example 12
The preparation method of the modified ball clay adopts the following technical scheme:
s1: crushing and sieving the ball clay to remove large-particle impurities, and drying to obtain ball clay powder;
s2: immersing the ball clay powder prepared in the step S1 in acid liquor, uniformly stirring, standing for 7 hours at 90 ℃, then precipitating to remove liquid, and washing and drying the solid to obtain a standby material; the acid solution is hydrochloric acid solution with the molar concentration of 2 mol/L;
s3: putting the spare material prepared in the step S2 and water into a stirring barrel with a stirring paddle, wherein the stirring speed of the stirring paddle is set to be 40r/min, and the stirring time is 20min, so as to prepare a ball clay solution; the mass ratio of the used standby materials to water is 1: 3;
s4: carrying out ultrasonic treatment on the ball clay solution prepared in the step S3 for 9 h;
s5: adding a coupling agent into the ball clay solution prepared in the step S4, setting the stirring speed of the stirring slurry to be 30r/min, and mixing and stirring for 15min to obtain a primary treatment material; the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 2.5: 1.5: 2.5; the mass ratio of the coupling agent to the ball clay solution is 1: 200;
s6: and (5) performing suction filtration and drying on the primary treated material prepared in the step S5 to obtain the catalyst.
Example 13
The preparation method of the modified ball clay adopts the following technical scheme:
s1: crushing ball clay, sieving to remove large particle impurities, and drying to obtain ball clay powder;
s2: putting the ball clay powder prepared in the step S1 and water into a stirring barrel with a stirring paddle, wherein the stirring speed of the stirring paddle is set to be 40r/min, and the stirring time is 20min, so as to prepare a ball clay solution; the mass ratio of the ball clay powder to the water is 1: 3;
s3: adding a coupling agent and an initiator into the ball clay solution prepared in the step S2, and then mixing and stirring for 15min to obtain a primary treatment material; the stirring speed of the stirring paddle is set to be 30 r/min; the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 2.5: 1.5: 2.5; the initiator is prepared from ammonium persulfate and sodium bisulfite according to a mass ratio of 3: 2, preparing a composition; the mass ratio of the coupling agent to the ball clay solution is 1: 200 of a carrier; the mass ratio of the initiator to the coupling agent is 1: 1;
s4: and (5) performing suction filtration and drying on the primary treated material prepared in the step S3 to obtain the catalyst.
Example 14
The method for producing a modified ball clay of this example differs from example 13 in that the initiator added in step S3 is prepared from ammonium persulfate and sodium bisulfite in a mass ratio of 4: 1, the rest being the same as in example 13.
Example 15
The method for preparing a modified ball clay of this example is different from example 13 in that the initiator added in step S3 is prepared from ammonium persulfate and sodium bisulfite in a mass ratio of 3.5: 1.5, the rest being the same as in example 13.
Example 16
The method for producing a modified ball clay of this example differs from example 15 in that the mass ratio of the initiator to the coupling agent added in step S3 is 3: 1, the rest is the same as in example 15.
Example 17
The method for producing a modified ball clay of this example differs from example 15 in that the mass ratio of the initiator to the coupling agent added in step S3 is 2.5: 1.5, the rest being the same as in example 15.
Example 18
The preparation method of the modified ball clay adopts the following technical scheme:
s1: crushing ball clay, sieving to remove large particle impurities, and drying to obtain ball clay powder;
s2: immersing the ball clay powder prepared in the step S1 in acid liquor, uniformly stirring, standing for 7h at 90 ℃, then precipitating to remove liquid, washing and drying the solid to prepare a standby material; the acid solution is hydrochloric acid solution with the molar concentration of 2 mol/L;
s3: putting the spare material prepared in the step S2 and water into a stirring barrel with a stirring paddle, wherein the stirring speed of the stirring paddle is set to be 40r/min, and the stirring time is 20min, so as to prepare a ball clay solution; the mass ratio of the ball clay powder to the water is 1: 3;
s4: carrying out ultrasonic treatment on the ball clay solution prepared in the step S3 for 9 h;
s5: adding a coupling agent and an initiator into the ball clay solution prepared in the step S4, and then mixing and stirring for 15min to obtain a primary treatment material; the stirring speed of the stirring paddle is set to be 30 r/min; the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 2.5: 1.5: 2.5; the initiator is prepared from ammonium persulfate and sodium bisulfite according to the mass ratio of 3.5: 1.5; the mass ratio of the coupling agent to the ball clay solution is 1: 200 of a carrier; the mass ratio of the initiator to the coupling agent is 2.5: 1.5;
s6: and (4) performing suction filtration and drying on the primary treatment material prepared in the step S5 to obtain the catalyst.
Comparative example
Comparative example 1
The modified ball clay of this comparative example was prepared in the same manner as in example 1 except that gamma-glycidoxypropyltrimethoxysilane was used as the coupling agent, and the rest was the same as in example 1.
Comparative example 2
The modified ball clay of this comparative example was prepared in the same manner as in example 1 except that gamma-methacryloxypropyltrimethoxysilane was used as the coupling agent, and the remainder was the same as in example 1.
Comparative example 3
The modified ball clay of this comparative example was prepared in the same manner as in example 1 except that isopropyl tris (dioctyl pyrophosphato acyloxy) titanate was used as a coupling agent, and the remainder was the same as in example 1.
Comparative example 4
The modified ball clay of this comparative example was prepared in a manner different from that of example 1 in that the coupling agent used was a mixture of gamma-glycidoxypropyltrimethoxysilane and isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 6: 1, the rest being the same as in example 1.
Performance test
Test method
1. Respectively mixing the modified ball clay prepared in examples 1-18 and comparative examples 1-4 with rubber according to the mass ratio of 1:80 to prepare samples;
2. respectively putting the samples prepared in the step 1 on a double-roll open mill for plastication, wherein the roll temperature is 55 ℃, and the roll distance is 20mm, so as to prepare a primary treatment material;
3. and (3) putting the primary treatment material prepared in the step (2) into a vulcanizing machine, and vulcanizing at 155 ℃ for 30min to prepare a test sample strip.
The test bars containing the modified ball clays prepared in examples 1 to 18 and comparative examples 1 to 4 were subjected to tensile strength test by the method of GB/T528-1998, the test results are shown in Table 1;
TABLE 1 tensile Strength test results of test specimens prepared in examples 1 to 18 and comparative examples 1 to 4
Serial number Tensile Strength (MPa)
Example 1 15.8
Example 2 16.1
Example 3 16.4
Example 4 16.3
Example 5 16.8
Example 6 16.6
Example 7 17.4
Example 8 16.1
Example 9 18.0
Example 10 17.9
Example 11 18.6
Example 12 19.2
Example 13 19.0
Example 14 19.3
Example 15 19.8
Example 16 20.1
Example 17 21.4
Example 18 24.2
Comparative example 1 14.7
Comparative example 2 14.2
Comparative example 3 13.9
Comparative example 4 15.2
As can be seen by combining examples 1 to 7 and comparative examples 1 to 4 with Table 1, when the coupling agent was added from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, isopropyltris (dioctylpyrophosphate) titanate in a mass ratio of 2.5: 1.5: 2.5, the surface of the ball clay is modified by gamma-glycidyl ether oxypropyl trimethoxy silane, so that the adhesive property of the ball clay and rubber is improved, and the filling and reinforcing effects of the subsequent ball clay and rubber are further improved; the gamma-methacryloxypropyltrimethoxysilane is used for carrying out surface modification on the ball clay, so that the adhesive force between the modified ball clay and the rubber is improved, and the durability of the rubber is also improved; after the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate modified ball clay is filled into rubber, the processability of the rubber can be improved, and the reinforcing effect on the rubber is better through the combined action of gamma-glycidyl ether oxypropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
It can be seen by combining examples 11-12 and comparative examples 1-4 with table 1 that when the ultrasonic treatment is performed before the coupling agent is added to the ball clay solution, the contact area between the subsequent ball clay and the coupling agent is increased, and the effect of the coupling agent on modifying the ball clay is improved.
Combining examples 13-17 and comparative examples 1-4 with table 1, it can be seen that after the coupling agent is added to the ball clay solution, an initiator is added, when the initiator is prepared from ammonium persulfate and sodium bisulfite in a mass ratio of 3.5: 1.5, initiating active groups on the surface of the ball clay by utilizing redox reaction of ammonium persulfate and sodium bisulfite in the ball clay solution, so that the chemical bonding process between the coupling agent and the ball clay is smoother; meanwhile, when the mass ratio of the initiator to the coupling agent is 2.5: 1.5, the modified ball clay has the best filling and reinforcing effects on rubber.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (6)

1. The preparation method of the modified ball clay is characterized by comprising the following steps:
s1: crushing, sieving and drying the ball clay to obtain ball clay powder;
s2: mixing the ball clay powder prepared in the step S1 with water according to the mass ratio of 1: (2-3) preparing a ball clay solution; after the ball clay powder is prepared in step S1, before the ball clay powder is mixed with water, the method further includes the following steps: soaking the ball clay powder in acid liquor, precipitating, separating, washing and drying; the acid solution is hydrochloric acid;
s3: adding a coupling agent into the ball clay solution prepared in the step S2, and mixing to obtain a primary treatment material; the coupling agent is at least one of gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of (3-5): (2-3); after the coupling agent is added to the ball clay solution in step S3, before mixing, the method further comprises the following steps: adding an initiator into the ball clay solution, wherein the initiator is prepared from ammonium persulfate and sodium bisulfite according to a mass ratio of (3-4): (1-2);
s4: and (5) performing suction filtration on the primary treated material prepared in the step (S3), and drying to obtain the product.
2. The process for producing a modified ball clay according to claim 1, characterized in that: the coupling agent is prepared from gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of (2-3): (1-2): (2-3).
3. The process for producing a modified ball clay according to claim 2, characterized in that: the mass ratio of the coupling agent to the ball clay solution in the step S3 is (1-2): (200-300).
4. The process for producing a modified ball clay according to claim 1, wherein: before adding the coupling agent into the ball clay solution in the step S3, the method further includes the following steps: and (3) carrying out ultrasonic treatment on the ball clay solution for 8-10 h.
5. The process for producing a modified ball clay according to claim 1, characterized in that: the mass ratio of the initiator to the coupling agent is (2-3): (1-2).
6. A modified ball clay prepared by the method for preparing the modified ball clay according to any one of claims 1 to 5.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1890311A (en) * 2003-12-05 2007-01-03 陶氏康宁公司 Method of making kaolin containing silicone rubber compositions
CN1970607A (en) * 2006-11-22 2007-05-30 北京化工大学 Silane coupling agent modified clay and butadiene styrene rubber nanometer composite material preparation method
CN101128264A (en) * 2004-12-23 2008-02-20 佐治亚-太平洋化学有限责任公司 Modified amine-aldehyde resins and uses thereof in separation processes
CN101230210A (en) * 2007-12-28 2008-07-30 河北工业大学 Method for preparing organic modified silicate mineral clay
CN101381488A (en) * 2008-11-04 2009-03-11 中国矿业大学(北京) Kaolin/rubber nano compound material with strengthening and obstructing dual property
JP2013112764A (en) * 2011-11-30 2013-06-10 Sumitomo Chemical Co Ltd Method for producing resin composite material
CN104017360A (en) * 2014-06-27 2014-09-03 南京化工职业技术学院 Organic clay synergic flame-retardant PA6 (polyamide 6) composite material and preparation method thereof
CN105482223A (en) * 2015-12-16 2016-04-13 湖北蓝盾之星科技有限公司 High-strength high-elongation and high-density polyethylene geomembrane and preparation method thereof
CN106495493A (en) * 2016-10-11 2017-03-15 常州市鼎日环保科技有限公司 A kind of preparation method of crystallite stone ceramic tile
CN111019404A (en) * 2019-11-29 2020-04-17 淮阴工学院 Modified attapulgite for rubber reinforcement and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1890311A (en) * 2003-12-05 2007-01-03 陶氏康宁公司 Method of making kaolin containing silicone rubber compositions
CN101128264A (en) * 2004-12-23 2008-02-20 佐治亚-太平洋化学有限责任公司 Modified amine-aldehyde resins and uses thereof in separation processes
CN1970607A (en) * 2006-11-22 2007-05-30 北京化工大学 Silane coupling agent modified clay and butadiene styrene rubber nanometer composite material preparation method
CN101230210A (en) * 2007-12-28 2008-07-30 河北工业大学 Method for preparing organic modified silicate mineral clay
CN101381488A (en) * 2008-11-04 2009-03-11 中国矿业大学(北京) Kaolin/rubber nano compound material with strengthening and obstructing dual property
JP2013112764A (en) * 2011-11-30 2013-06-10 Sumitomo Chemical Co Ltd Method for producing resin composite material
CN104017360A (en) * 2014-06-27 2014-09-03 南京化工职业技术学院 Organic clay synergic flame-retardant PA6 (polyamide 6) composite material and preparation method thereof
CN105482223A (en) * 2015-12-16 2016-04-13 湖北蓝盾之星科技有限公司 High-strength high-elongation and high-density polyethylene geomembrane and preparation method thereof
CN106495493A (en) * 2016-10-11 2017-03-15 常州市鼎日环保科技有限公司 A kind of preparation method of crystallite stone ceramic tile
CN111019404A (en) * 2019-11-29 2020-04-17 淮阴工学院 Modified attapulgite for rubber reinforcement and preparation method thereof

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