CN108409899B - Preparation method of cerium salt initiated attapulgite/polyacrylic acid composite thickener - Google Patents

Preparation method of cerium salt initiated attapulgite/polyacrylic acid composite thickener Download PDF

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CN108409899B
CN108409899B CN201810118693.2A CN201810118693A CN108409899B CN 108409899 B CN108409899 B CN 108409899B CN 201810118693 A CN201810118693 A CN 201810118693A CN 108409899 B CN108409899 B CN 108409899B
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attapulgite
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polyacrylic acid
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CN108409899A (en
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彭勇刚
纪俊玲
陶永新
万怀新
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents

Abstract

The invention belongs to the field of new materials, and particularly relates to a preparation method of a cerium salt initiated attapulgite/polyacrylic acid composite thickener4+The strong oxidizing property of the attapulgite/polyacrylic acid composite thickening agent forms an oxidation-reduction initiation system, the oxidation-reduction initiation system is used for initiating acrylic acid monomers, an inverse emulsion polymerization mode is adopted, the attapulgite/polyacrylic acid composite thickening agent is prepared, and the thickening agent is excellent in thickening performance and good in electrolyte resistance.

Description

Preparation method of cerium salt initiated attapulgite/polyacrylic acid composite thickener
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method of a cerium salt initiated attapulgite/polyacrylic acid composite thickener.
Background
The thickener is an important component of the printing paste. The polyacrylic acid thickener has strong thickening capacity and wide application range; but the polyacrylic acid thickener has poor electrolyte resistance and high use cost. The attapulgite is a porous chain lamellar water-containing magnesium aluminum silicate-rich clay mineral, and the attapulgite is compounded with the polyacrylic acid thickening agent, so that the production cost of the polyacrylic acid thickening agent can be reduced, and the electrolyte resistance of the polyacrylic acid thickening agent can be improved. However, the attapulgite is an inorganic material, has poor compatibility with organic polymers, and how to realize organic combination of the attapulgite and the organic polymers to prepare the attapulgite/polyacrylic acid composite thickening agent with excellent performance is always the direction of efforts of material scientists.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a cerium salt initiated attapulgite/polyacrylic acid composite thickener4+The strong oxidizing property of the attapulgite/polyacrylic acid composite thickening agent forms an oxidation-reduction type initiation system, and the oxidation-reduction type initiation system is used for initiating acrylic acid monomers to prepare the attapulgite/polyacrylic acid composite thickening agent by adopting a reverse emulsion polymerization mode. The good thixotropy of the attapulgite and the synergistic effect of the organic polymer thickening agent achieve advantage complementation.
The technical scheme for realizing the purpose is as follows: a cerium salt initiated attapulgite/polyacrylic acid composite thickening agent is prepared by modifying attapulgite with silane coupling agent, introducing mercapto group on surface, and mixing with Ce4+Constitute an oxidation-reduction initiation system for the initiated polymerization of acrylic monomers.
The invention provides a preparation method of a cerium salt initiated attapulgite/polyacrylic acid composite thickener, which comprises the following steps:
(1) dispersing attapulgite in an organic solvent according to a solid-liquid mass ratio of 1:100-4:100, performing ultrasonic dispersion for 30-60min, dropwise adding a silane coupling agent, stirring under the protection of nitrogen, performing heating reflux reaction for 12-24h, removing the solvent after the reaction is finished, performing vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
wherein the organic solvent is toluene or xylene; the silane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, and the mass ratio of the silane coupling agent to the attapulgite is 2:1-5: 1;
(2) putting a four-mouth flask into a cold water bath, adding an unsaturated acid monomer and mercapto attapulgite, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30-60min to obtain a water phase substance, wherein the mercapto attapulgite accounts for 20-40% of the mass of the unsaturated acid monomer; preparing an oil phase from an emulsifier, a cross-linking agent and an organic solvent, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1500 rpm for 60-90min at 1000 rpm, heating to 50-60 ℃, dropwise adding an initiator aqueous solution under the stirring condition of 450 rpm at 300 rpm, continuously heating to 60-70 ℃ after dropwise adding, reacting for 1-3h, cooling and discharging after the reaction is finished, and then adding the phase transfer agent and uniformly stirring to obtain a finished product.
Wherein, the unsaturated acid monomer is one or any combination of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and maleic anhydride.
Wherein the emulsifier is sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester, and the dosage of the emulsifier accounts for 2-8% of the mass of the unsaturated acid monomer.
The crosslinking agent is diallyl phthalate, and the mass of the crosslinking agent accounts for 0.1-0.25% of the mass of the unsaturated acid monomer.
The organic solvent is one of 120# gasoline, 200# gasoline, kerosene and 5# white oil, and the mass ratio of the unsaturated acidic monomer to the organic solvent is 0.25:1-0.6: 1.
The initiator is ammonium ceric sulfate or ammonium ceric nitrate, and the mass of the initiator accounts for 0.5-1.0% of that of the unsaturated acid monomer.
The phase transfer agent is isomeric tridecanol polyoxyethylene ether or fatty alcohol polyoxyethylene ether, and the dosage of the phase transfer agent accounts for 4-6% of the mass of the unsaturated acidic monomer.
The invention has the beneficial effects that: by utilizing the reducibility of mercapto on the surface of attapulgite and Ce4+The strong oxidizing property of the attapulgite clay is used for forming an oxidation-reduction type initiation system to initiate polymerization, the compatibility of the attapulgite clay and the organic polymer is good, and the thickening performance and the electrolyte resistance of the obtained thickening agent are excellent.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
(1) Dispersing attapulgite in toluene according to the solid-liquid mass ratio of 1:100, ultrasonically dispersing for 30min, dropwise adding 3-mercaptopropyl trimethoxy silane, wherein the mass ratio of the 3-mercaptopropyl trimethoxy silane to the attapulgite is 2:1, stirring under the protection of nitrogen, heating, refluxing and reacting for 12h, removing the solvent after the reaction is finished, carrying out vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
(2) placing a four-mouth flask in a cold water bath, adding acrylic acid and mercapto attapulgite, wherein the mercapto attapulgite accounts for 20% of the mass of the acrylic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30min to obtain a water phase substance; preparing an oil phase from sorbitan fatty acid ester, diallyl phthalate and 120# gasoline, wherein the dosage of the sorbitan fatty acid ester accounts for 2% of the mass of acrylic acid, the dosage of the diallyl phthalate accounts for 0.1% of the mass of the acrylic acid, the mass ratio of the acrylic acid to the 120# gasoline is 0.25:1, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1000 r/min for 90min, heating to 50 ℃, dropwise adding an initiator ammonium cerium sulfate aqueous solution under the stirring condition of 300 r/min, wherein the mass of the ammonium cerium sulfate accounts for 0.5% of the mass of the acrylic acid, after dropwise adding, continuously heating to 60 ℃, reacting for 3h, cooling and discharging after the reaction is finished, then adding a phase transfer agent namely isotridecanol polyoxyethylene ether, the dosage of which accounts for 4% of the mass of the acrylic acid, and uniformly stirring to obtain.
Comparative example 1
Placing a four-mouth flask in a cold water bath, adding acrylic acid and attapulgite, wherein the attapulgite accounts for 20% of the mass of the acrylic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30min to obtain a water phase substance; preparing an oil phase from sorbitan fatty acid ester, diallyl phthalate and 120# gasoline, wherein the dosage of the sorbitan fatty acid ester accounts for 2% of the mass of acrylic acid, the dosage of the diallyl phthalate accounts for 0.1% of the mass of the acrylic acid, the mass ratio of the acrylic acid to the 120# gasoline is 0.25:1, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1000 r/min for 90min, heating to 50 ℃, dropwise adding an initiator ammonium cerium sulfate aqueous solution under the stirring condition of 300 r/min, wherein the mass of the ammonium cerium sulfate accounts for 0.5% of the mass of the acrylic acid, after dropwise adding, continuously heating to 60 ℃, reacting for 3h, cooling and discharging after the reaction is finished, then adding a phase transfer agent namely isotridecanol polyoxyethylene ether, the dosage of which accounts for 4% of the mass of the acrylic acid, and uniformly stirring to obtain.
Comparative example 2a
Placing a four-mouth flask in a cold water bath, adding acrylic acid and attapulgite, wherein the attapulgite accounts for 20% of the mass of the acrylic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30min to obtain a water phase substance; preparing an oil phase from sorbitan fatty acid ester, diallyl phthalate and 120# gasoline, wherein the amount of the sorbitan fatty acid ester accounts for 2% of the mass of acrylic acid, the amount of the diallyl phthalate accounts for 0.1% of the mass of the acrylic acid, the mass ratio of the acrylic acid to the 120# gasoline is 0.25:1, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1000 r/min for 90min, heating to 50 ℃, dropwise adding an initiator ammonium persulfate aqueous solution under the stirring condition of 300 r/min, wherein the mass of the ammonium persulfate accounts for 0.5% of the mass of the acrylic acid, after dropwise adding, continuously heating to 60 ℃, reacting for 3h, cooling and discharging after the reaction is finished, then adding a phase transfer agent isomeric tridecanol polyoxyethylene ether, the amount of which accounts for 4% of the mass of the acrylic acid, and uniformly stirring to obtain.
Comparative example 2b
Placing the four-neck flask in a cold water bath, adding acrylic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30min to obtain a water phase substance; preparing an oil phase from sorbitan fatty acid ester, diallyl phthalate and 120# gasoline, wherein the amount of the sorbitan fatty acid ester accounts for 2% of the mass of acrylic acid, the amount of the diallyl phthalate accounts for 0.1% of the mass of the acrylic acid, the mass ratio of the acrylic acid to the 120# gasoline is 0.25:1, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1000 r/min for 90min, heating to 50 ℃, dropwise adding an initiator ammonium persulfate aqueous solution under the stirring condition of 300 r/min, wherein the mass of the ammonium persulfate accounts for 0.5% of the mass of the acrylic acid, after dropwise adding, continuously heating to 60 ℃, reacting for 3h, cooling and discharging after the reaction is finished, then adding a phase transfer agent isomeric tridecanol polyoxyethylene ether, the amount of which accounts for 4% of the mass of the acrylic acid, and uniformly stirring to obtain.
Example 2
(1) Dispersing attapulgite in xylene according to a solid-liquid mass ratio of 4:100, ultrasonically dispersing for 60min, dropwise adding 3-mercaptopropyltriethoxysilane, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the attapulgite is 5:1, stirring under the protection of nitrogen, heating, refluxing and reacting for 24h, removing a solvent after the reaction is finished, carrying out vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
(2) placing a four-mouth flask in a cold water bath, adding methacrylic acid and mercapto attapulgite, wherein the mass of the mercapto attapulgite accounts for 40% of that of the methacrylic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 60min to obtain a water phase substance; preparing polyoxyethylene sorbitan fatty acid ester, diallyl phthalate and 200# gasoline into an oil phase, wherein the polyoxyethylene sorbitan fatty acid ester accounts for 8% of the mass of methacrylic acid, the diallyl phthalate accounts for 0.25% of the mass of a methacrylic acid monomer, the mass ratio of the methacrylic acid to the 200# gasoline is 0.6:1, adding a water phase into the oil phase under the stirring condition, emulsifying at a high speed of 1500 r/min for 60min, heating to 60 ℃, dropwise adding a cerium ammonium nitrate aqueous solution under the stirring condition of 450 r/min, wherein the mass of the cerium ammonium nitrate accounts for 1.0% of the mass of the methacrylic acid monomer, after the dropwise adding is finished, continuously heating to 70 ℃, reacting for 1h, cooling and discharging after the reaction is finished, then adding fatty alcohol polyoxyethylene ether, the amount of which accounts for 6% of the mass of the methacrylic acid monomer, and uniformly stirring to obtain a finished product.
Example 3
(1) Dispersing attapulgite in toluene according to the solid-liquid mass ratio of 2:100, ultrasonically dispersing for 40min, dropwise adding 3-mercaptopropyl trimethoxy silane, wherein the mass ratio of the 3-mercaptopropyl trimethoxy silane to the attapulgite is 3:1, stirring under the protection of nitrogen, heating, refluxing and reacting for 16h, removing the solvent after the reaction is finished, carrying out vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
(2) putting a four-mouth flask into a cold water bath, adding itaconic acid and mercapto attapulgite, wherein the mass of the mercapto attapulgite accounts for 30% of that of the itaconic acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 40min to obtain a water phase substance; preparing an oil phase from sorbitan fatty acid ester, diallyl phthalate and kerosene, wherein the sorbitan fatty acid ester accounts for 4% of the mass of itaconic acid, the diallyl phthalate accounts for 0.15% of the mass of itaconic acid, the mass ratio of itaconic acid to kerosene is 0.4:1, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1200 r/min for 70min, heating to 55 ℃, dropwise adding a cerium ammonium sulfate aqueous solution under the stirring condition of 350 r/min, heating to 65 ℃ after dropwise adding, reacting for 2h, cooling and discharging after the reaction is finished, adding isotridecanol polyoxyethylene ether, the amount of which accounts for 5% of the mass of itaconic acid, and stirring uniformly to obtain a finished product.
Example 4
(1) Dispersing attapulgite in xylene according to the solid-liquid mass ratio of 3:100, ultrasonically dispersing for 50min, dropwise adding 3-mercaptopropyltriethoxysilane, wherein the mass ratio of the 3-mercaptopropyltriethoxysilane to the attapulgite is 4:1, stirring under the protection of nitrogen, heating for reflux reaction for 20h, removing a solvent after the reaction is finished, carrying out vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
(2) placing a four-mouth flask in a cold water bath, adding fumaric acid and mercapto attapulgite, wherein the mass of the mercapto attapulgite accounts for 35% of that of the fumaric acid, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 50min to obtain a water phase substance; preparing polyoxyethylene sorbitan fatty acid ester, dipropylene phthalate and 5# white oil into an oil phase, wherein the amount of the polyoxyethylene sorbitan fatty acid ester accounts for 6% of the mass of fumaric acid, the mass of the dipropylene phthalate accounts for 0.2% of the mass of the fumaric acid, and the mass ratio of the fumaric acid to the 5# white oil is 0.5:1, adding an aqueous phase into the oil phase under the stirring condition, emulsifying at a high speed of 1300 r/min for 80min, heating to 58 ℃, dropwise adding a cerium ammonium nitrate aqueous solution under the stirring condition of 400 r/min, wherein the cerium ammonium nitrate accounts for 0.8% of the mass of the fumaric acid, after the dropwise adding, continuously heating to 68 ℃, reacting for 2.5h, cooling after the reaction is finished, discharging, then adding fatty alcohol polyoxyethylene ether, wherein the mass of the fatty alcohol polyoxyethylene ether accounts for 5.5% of the mass of the fumaric acid, and uniformly stirring to obtain a finished product.
Example 5
Accurately weighing 2g of thickening agent, adding 98g of distilled water, stirring, dropwise adding 3-4 drops of ammonia water, and fully stirring to prepare white slurry with the mass fraction of 2%. The viscosity of the white slurry was measured at room temperature using a Brookfield DV-II + Pro viscometer at a constant speed of 10 rpm (spindle 6).
The electrolyte resistance was measured as the viscosity retention of 0.05% NaCl (solids) added to the thickener white slurry, which was ηAfter adding NaCl/ηBefore adding NaClThe higher the viscosity retention, the better the electrolyte resistance.
TABLE 1 thickening Properties of the samples
Figure BDA0001571426630000051
As can be seen from the above table, the thickeners obtained in examples 1 to 4 have strong thickening ability and excellent electrolyte resistance. In comparative example 1, since the attapulgite was not modified with the mercaptosilane coupling agent, the ammonium cerium sulfate did not initiate complete polymerization of the acrylic monomer, and the resulting thickener had poor thickening performance. Comparative example 2a the polymerization of monomers was initiated using conventional ammonium persulfate, and the resulting product, although having better thickening and electrolyte resistance properties, was still slightly inferior to that of example 1, probably due to the poor dispersion of the attapulgite in the polyacrylic acid. In comparative example 2b, the product obtained had a slightly inferior thickening property and poor electrolyte resistance, since attapulgite was not added.

Claims (8)

1. A preparation method of a cerium salt initiated attapulgite/polyacrylic acid composite thickener is characterized by comprising the following steps: firstly, introducing sulfydryl on the surface of the attapulgite, and utilizing the reducibility of the sulfydryl and Ce4+The strong oxidizing property of the attapulgite/polyacrylic acid composite thickening agent forms an oxidation-reduction type initiation system, and the oxidation-reduction type initiation system is used for initiating monomers to prepare the attapulgite/polyacrylic acid composite thickening agent in an inverse emulsion polymerization mode; wherein, the monomer is one or any combination of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and maleic anhydride.
2. The method of claim 1, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the method comprises the specific steps of carrying out the following steps,
(1) dispersing attapulgite in an organic solvent according to a solid-liquid mass ratio of 1:100-4:100, performing ultrasonic dispersion for 30-60min, dropwise adding a silane coupling agent, stirring under the protection of nitrogen, performing heating reflux reaction for 12-24h, removing the solvent after the reaction is finished, performing vacuum drying, grinding, and sieving with a 200-mesh sieve to obtain mercapto attapulgite;
(2) putting a four-mouth flask into a cold water bath, adding a monomer and mercapto attapulgite, wherein the mercapto attapulgite accounts for 20-40% of the mass of the monomer, slowly dropwise adding ammonia water until the pH value of the solution is 6, and stirring at 500 rpm for 30-60min to obtain a water phase substance; preparing an oil phase from an emulsifier, a cross-linking agent and an organic solvent, adding a water phase material into the oil phase under the stirring condition, emulsifying at a high speed of 1500 rpm for 60-90min at 1000 rpm, heating to 50-60 ℃, dropwise adding an initiator aqueous solution under the stirring condition of 450 rpm at 300 rpm, continuously heating to 60-70 ℃ after dropwise adding, reacting for 1-3h, cooling and discharging after the reaction is finished, and then adding the phase transfer agent and uniformly stirring to obtain a finished product.
3. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the organic solvent in the step (1) is toluene or xylene; the silane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, and the mass ratio of the silane coupling agent to the attapulgite is 2:1-5: 1.
4. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the emulsifier in the step (2) is sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester, and the dosage of the emulsifier accounts for 2-8% of the mass of the monomer.
5. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the cross-linking agent in the step (2) is diallyl phthalate, and the mass of the cross-linking agent accounts for 0.1-0.25% of the mass of the monomer.
6. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the organic solvent in the step (2) is one of 120# gasoline, 200# gasoline, kerosene and 5# white oil, and the mass ratio of the monomer to the organic solvent is 0.25:1-0.6: 1.
7. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the initiator in the step (2) is ammonium ceric sulfate or ammonium ceric nitrate, and the mass of the initiator accounts for 0.5-1.0% of the mass of the monomer.
8. The method of claim 2, wherein the cerium salt-initiated attapulgite/polyacrylic acid composite thickener comprises: the phase transfer agent in the step (2) is isomeric tridecanol polyoxyethylene ether or fatty alcohol polyoxyethylene ether, and the dosage of the phase transfer agent accounts for 4-6% of the mass of the monomer.
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CN102443120A (en) * 2011-08-15 2012-05-09 中北大学 Method for realizing efficient graft polymerization of acrylonitrile on surface of silica gel microparticles by utilizing mercapto-Ce(IV) salt redox initiation system
CN105061662A (en) * 2015-08-11 2015-11-18 常州大学 Preparation method of acrylic thickening agents with inorganic clay as cross-linking agent

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CN102443120A (en) * 2011-08-15 2012-05-09 中北大学 Method for realizing efficient graft polymerization of acrylonitrile on surface of silica gel microparticles by utilizing mercapto-Ce(IV) salt redox initiation system
CN105061662A (en) * 2015-08-11 2015-11-18 常州大学 Preparation method of acrylic thickening agents with inorganic clay as cross-linking agent

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