CN101195717A - Organic surface modifying method of attapulgite - Google Patents
Organic surface modifying method of attapulgite Download PDFInfo
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Abstract
The invention relates to a modification method of the organic surface of attapulgite. The process steps are as follows: the attapulgite powder is added into deionized water according to certain proportion, so as to produce attapulgite suspendion liquid, and the attapulgite mass occupies 5 percent to 25 percent of the water mass; the temperature of the attapulgite suspendion liquid is adjusted to be 20 to 90 DEG C, cationic surface active agent is added, the cationic surface active agent quality is 2 to 10 percent of the attapulgite quality, and stirring and reaction are perfromed for 2 to 10 h; after the organic surface modification of the cationic surface active agent is accomplished, the pH value of the system is adjusted to be 3 to 3 or 8 to 11, silane coupling agent is added into the reaction system, the silane coupling agent mass occupies 5 to 20 percent of the attapulgite mass, and the the silane coupling agent is stirred and reacted for 3 to 24 h below 20 to 90 DEG C; the obtained attapulgite pulp is filtered, washed, dried and crushed, and finally the attapulgite powder modified through combing the cationic surface active agent with the silane coupling agent is obtained. Through the cationic surface active agent and the silane coupling agent to perform the organic surface modification to the attapulgite together, the organic surface modification effect is greatly improved.
Description
Technical field
The present invention relates to a kind of organic surface modifying method of attapulgite, be specially the collaborative novel method of attapulgite being carried out organic surface modifying of a kind of cats product and silane coupling agent.
Background technology
Attapulgite is a kind of natural nano layer chain silicate, has fibrous crystalline structure, and length-to-diameter ratio is very big, and its constitutional features belongs to monodimension nanometer material, is the desirable supporting material of macromolecular material.Attapulgite's surface is wetting ability, only is suitable for using in the polar system.Be difficult in the organic systems such as plastics, rubber, chemical fibre, solvent based coating disperse but add, can not embody the specific function of attapulgite.For improving consistency and the dispersiveness of attapulgite in organic system, improve the performance of adding nano-attapulgite clay compounded system, must carry out organic surface modifying to nano-attapulgite.Because attapulgite's surface contains a large amount of silicon hydroxyls and electronegative, usually with coupling agent or cats product to the nano-attapulgite surface modification that organises.For example: employing vinyltriethoxysilanes such as Song Renfeng have carried out finishing (silicate circular, 2003 the 3rd phases to nano-attapulgite; China's plastics, 2002 the 7th phases); Huang Jianhua etc. adopt octadecyl trimethyl ammonium chloride attapulgite modified (Chinese oil, 2005 the 2nd phases; Wang Yunpu adopts palmityl trimethyl ammonium chloride attapulgite modified (nonmetalliferous ore, 2005 the 6th phases).CN1793242A proposes a kind of preparation method of attapulgite of cats product modification, it is raw material with the attapulgite, carry out acid treatment, obtain the acidifying attapulgite, then, carry out ion-exchange with sodium ion in the sodium-chlor, obtain the attapulgite of sodium, at last, the sodium ion between the fiber of employing ultrasonic wave promotion cats product and attapulgite carries out cationic exchange, obtains the attapulgite of cats product modification.CN1843911A proposes a kind of preparation method of silane coupler modified attapulgite, with the attapulgite is raw material, carry out acid treatment, obtain the acidifying attapulgite, then, carry out ultrasonic dispersing, silane coupling agent is hydrolyzed, at last, silane coupling agent hydrolyzed solution and attapulgite carry out dehydration condensation, obtain silane coupler modified attapulgite.Adopting the cats product modification is to utilize the electronegative under normal conditions character of attapulgite's surface; Adopting silane coupler modified then is the silicon hydroxyl that utilizes attapulgite's surface.Because aforesaid method has only utilized an aspect of attapulgite's surface character to carry out organic surface modifying, modified effect is unsatisfactory.The hydrophobicity that shows as the attapulgite after the modification on the macroscopic view is relatively poor, can not bubble through the water column fully.
Summary of the invention
The purpose of this invention is to provide a kind of organic surface modifying method of attapulgite, this method can improve organic surface modifying greatly and change fruit.
The technical scheme that realizes above-mentioned purpose is: a kind of organic surface modifying method of attapulgite, and processing step is as follows:
(1) preparation of attapulgite suspension: the attapulgite powder is joined in the deionized water by a certain percentage, make attapulgite suspension, the attapulgite quality accounts for 5%～25% of quality;
(2) cats product is to the organic surface modifying of attapulgite: is the temperature regulation of attapulgite suspension 20～90 ℃, add cats product, the cats product quality accounts for 2～10% of attapulgite quality, stirring reaction 2～10h;
(3) silane coupling agent is to the organic surface modifying of attapulgite: after the cats product organic surface modifying finishes, pH value to 3～5 or 8～11 of regulation system, in reaction system, add silane coupling agent, the silane coupling agent quality accounts for 5～20% of attapulgite quality, at 20～90 ℃ of following stirring reaction 3～24h;
(4) organically-modified aftertreatment: with the attapulgite slurry by filtration of gained, washing, dry, pulverizing finally obtains the attapulgite powder through cats product and silane coupling agent modified synergic.
The cats product that is adopted is the organic ammonium salt, be specially the octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, the tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, two octyl alkyl dimethyl ammonium chlorides, two nonyl alkyl dimethyl ammonium chlorides, two octyl dimethyl brometo de amonios, two nonyl dimethyl brometo de amonios, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chlorides, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, distearyl dimethyl ammonium chloride, two ten alkyl dimethyl brometo de amonios, didodecyldimethylammbromide bromide, two tetradecyl dimethyl brometo de amonios, double hexadecyl dimethyl brometo de amonio, two octadecyl dimethyl brometo de amonios, tri-n-octyl methyl ammonium chloride, three nonyl ammonio methacrylates, trioctylphosphine methyl brometo de amonio, three nonyl methyl brometo de amonios, three (ten alkyl) ammonio methacrylate, three (dodecyl) ammonio methacrylate, three (tetradecyl) ammonio methacrylate, three (hexadecyl) ammonio methacrylate, three (octadecyl) ammonio methacrylate, three (ten alkyl) methyl brometo de amonio, three (dodecyl) methyl brometo de amonio, three (tetradecyl) methyl brometo de amonio, three (hexadecyl) methyl brometo de amonio, three (octadecyl) methyl brometo de amonio, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tripropyl brometo de amonio, benzyl tributyl brometo de amonio, the phenyl trimethyl ammonium chloride, a kind of in the phenyl trimethylammonium bromide.
The silane coupling agent that is adopted is an organoalkoxysilane, organoalkoxysilane is a methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the isobutyl-Trimethoxy silane, the isobutyl-triethoxyl silane, the n-hexyl triethoxyl silane, the n-octyl Trimethoxy silane, the n-octyl triethoxyl silane, isooctyltrimethoxysi,ane, the iso-octyl triethoxyl silane, the dodecyl Trimethoxy silane, the n-hexadecyl Trimethoxy silane, Octadecane base Trimethoxy silane, phenyl triethoxysilane, dimethoxydiphenylsilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-dimethyl base oxethyl silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, the propenyl Trimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, α-thiopurine methyltransferase triethoxyl silane, γ-mercapto propyl group methyl dimethoxysilane, γ-mercapto propyl group methyldiethoxysilane, two-[γ-(triethoxysilicane) propyl group] disulphide, a kind of in two-[γ-(triethoxysilicane) propyl group] tetrasulfide.
The present invention is electronegative and have a special property of a large amount of silicon hydroxyls according to attapulgite's surface, successively work in coordination with attapulgite is carried out organic surface modifying with cats product and silane coupling agent, its advantage is: modification changes fruit and is better than separately with the cats product modification or uses silane coupler modified modified effect separately, is in particular in that the hydrophobicity of the attapulgite after the modification of employing present method obviously improves.Activation index (H) through some attapulgite products of present method modification can reach 100%, has complete hydrophobicity.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment.
At first, the organic surface modifying effect of products obtained therefrom of the present invention is estimated by activation index (H).Attapulgite's surface is polarization state, can be easy to be dispersed in the water.If attapulgite's surface absorption or the agent of grafted organic surface modifying are nonpolar, the attapulgite's surface after surface modification treatment will be become nonpolar by polarity, and water is presented stronger non-infiltration.When the fine particle of this non-infiltration was in water, huge surface tension made it floating heavy as oil film.The activation index (H) of gained attapulgite powder is expressed as: floating part quality (g) in the H=sample/sample total mass (g) * 100%.
Embodiment 1
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the octadecyl trimethylammonium bromide of 0.1g, keep 90 ℃ of temperature of reaction, stirring reaction 2h.Add glacial acetic acid then, the pH=3 of regulation system adds γ-methacryloxypropyl trimethoxy silane of 1g again, continues stirring reaction 3h down at 90 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind octadecyl trimethylammonium bromide and the collaborative organic surface modifying of γ-methacryloxypropyl trimethoxy silane.The activation index H of gained powder is 100%.
Comparative example 1:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension heat to 90 ℃, add the octadecyl trimethylammonium bromide of 1g, keep 90 ℃ of temperature of reaction, stirring reaction 2h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind octadecyl trimethylammonium bromide organic surface modifying.The activation index H of gained powder is 0.
Comparative example 2:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds glacial acetic acid, the pH=3 of regulation system, γ-methacryloxypropyl trimethoxy silane of adding 1g is at 90 ℃ of following stirring reaction 3h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind γ-methacryloxypropyl trimethoxy silane organic surface modifying.The activation index H of gained powder is 0.
Embodiment 2:
At first in the 100g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.The attapulgite suspension temperature is adjusted to 20 ℃, adds the palmityl trimethyl ammonium chloride of 0.2g, keep 20 ℃ of temperature of reaction, stirring reaction 10h.The ammonia soln that adds 2mol/L then, the pH=8 of regulation system adds the methyltrimethoxy silane of 0.25g again, continues stirring reaction 24h down at 20 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind palmityl trimethyl ammonium chloride and the collaborative organic surface modifying of methyltrimethoxy silane.The activation index H of gained powder is 100%.
Comparative example 3:
At first in the 100g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.The attapulgite suspension temperature is adjusted to 20 ℃, adds the palmityl trimethyl ammonium chloride of 1g, keep 20 ℃ of temperature of reaction, stirring reaction 10h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind the palmityl trimethyl ammonium chloride organic surface modifying.The activation index H of gained powder is 0.
Comparative example 4:
At first in the 100g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.The attapulgite suspension temperature is adjusted to 20 ℃, adds the ammonia soln of 2mol/L, the pH=8 of regulation system, the methyltrimethoxy silane of adding 0.5g is at 20 ℃ of following stirring reaction 24h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind the methyltrimethoxy silane organic surface modifying.The activation index H of gained powder is 0.
Embodiment 3:
At first in the 50g deionized water, add 10g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the Trimethyllaurylammonium bromide of 0.5g, keep 90 ℃ of temperature of reaction, stirring reaction 6h.Add glacial acetic acid then, the pH=5 of regulation system adds the n-octyl Trimethoxy silane of 1.5g again, continues stirring reaction 4h down at 90 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind Trimethyllaurylammonium bromide and the collaborative organic surface modifying of n-octyl Trimethoxy silane.The activation index H of gained powder is 100%.
Comparative example 5:
At first in the 50g deionized water, add 10g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the Trimethyllaurylammonium bromide of 0.5g, keep 90 ℃ of temperature of reaction, stirring reaction 6h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind the Trimethyllaurylammonium bromide organic surface modifying.The activation index H of gained powder is 0.
Comparative example 6:
At first in the 50g deionized water, add 10g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds glacial acetic acid, the pH=5 of regulation system, the n-octyl Trimethoxy silane of adding 1.5g is at 90 ℃ of following stirring reaction 4h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind n-octyl Trimethoxy silane organic surface modifying.The activation index H of gained powder is 57%.
Embodiment 4:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the octadecyl trimethyl ammonium chloride of 0.5g, keep 90 ℃ of temperature of reaction, stirring reaction 4h.The ammonia soln that adds 2mol/L then, the pH=11 of regulation system adds the Octadecane base Trimethoxy silane of 1g again, continues stirring reaction 6h down at 90 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind octadecyl trimethyl ammonium chloride and the collaborative organic surface modifying of Octadecane base Trimethoxy silane.The activation index H of gained powder is 100%.
Comparative example 7:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the octadecyl trimethyl ammonium chloride of 0.5g, keep 90 ℃ of temperature of reaction, stirring reaction 4h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.At 110 ℃ oven drying, pulverize the attapulgite powder that promptly gets behind octadecyl trimethylammonium bromide organic surface modifying at last.The activation index H of gained powder is 0.
Comparative example 8:
At first in the 50g deionized water, add 5 g attapulgite powders, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the ammonia soln of 2mol/L, the pH=11 of regulation system, the Octadecane base Trimethoxy silane of adding 1g is at 90 ℃ of following stirring reaction 6h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.At 110 ℃ oven drying, pulverize the attapulgite powder that promptly gets behind Octadecane base Trimethoxy silane organic surface modifying at last.The activation index H of gained powder is 0.
Embodiment 5:
At first in the 50g deionized water, add 12.5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 70 ℃, adds the Dodecyl trimethyl ammonium chloride of 0.25g, keep 70 ℃ of temperature of reaction, stirring reaction 6h.Add glacial acetic acid then, the pH=4 of regulation system adds the iso-octyl triethoxyl silane of 1.25g again, continues stirring reaction 10h down at 70 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind Dodecyl trimethyl ammonium chloride and the collaborative organic surface modifying of iso-octyl triethoxyl silane.The activation index H of gained powder is 100%.
Comparative example 9:
At first in the 50g deionized water, add 12.5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 70 ℃, adds the Dodecyl trimethyl ammonium chloride of 2.5g, keep 70 ℃ of temperature of reaction, stirring reaction 6h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind the Dodecyl trimethyl ammonium chloride organic surface modifying.The activation index H of gained powder is 0.
Comparative example 10:
At first in the 50g deionized water, add 12.5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 70 ℃, adds glacial acetic acid, the pH=4 of regulation system adds the iso-octyl triethoxyl silane of 1.25g, again at 70 ℃ of following stirring reaction 10h.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind iso-octyl triethoxyl silane organic surface modifying.The activation index H of gained powder is 45%.
Embodiment 6:
At first in the 50g deionized water, add 10g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 60 ℃, adds two octyl alkyl dimethyl ammonium chlorides of 0.2g, keep 60 ℃ of temperature of reaction, stirring reaction 4h.Add glacial acetic acid then, the pH=4 of regulation system adds γ-mercapto propyl group methyldiethoxysilane of 2g again, continues stirring reaction 10h down at 60 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind two octyl alkyl dimethyl ammonium chlorides and the collaborative organic surface modifying of γ-mercapto propyl group methyldiethoxysilane.The activation index H of gained powder is 85%.
Embodiment 7:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 90 ℃, adds the cetyl trimethylammonium bromide of 0.15g, keep 90 ℃ of temperature of reaction, stirring reaction 2h.Add glacial acetic acid then, the pH=5 of regulation system adds two-[γ-(triethoxysilicane) propyl group] tetrasulfide of 0.75g again, continues stirring reaction 3h down at 90 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind cetyl trimethylammonium bromide and the collaborative organic surface modifying of two-[γ-(triethoxysilicane) propyl group] tetrasulfide.The activation index H of gained powder is 86%.
Embodiment 8:
At first in the 100g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 60 ℃, adds the dodecyl benzyl dimethyl ammonium chloride of 0.25g, keep 60 ℃ of temperature of reaction, stirring reaction 4h.Add glacial acetic acid then, the pH=3 of regulation system adds two-[γ-(triethoxysilicane) propyl group] disulphide of 1g again, continues stirring reaction 18h down at 60 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind dodecyl benzyl dimethyl ammonium chloride and the collaborative organic surface modifying of two-[γ-(triethoxysilicane) propyl group] disulphide.The activation index H of gained powder is 100%.
Embodiment 9:
At first in the 50g deionized water, add 10g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 40 ℃, adds three (dodecyl) ammonio methacrylate of 1g, keep 40 ℃ of temperature of reaction, stirring reaction 4h.The ammonia soln that adds 2mol/L then, the pH=8 of regulation system adds the phenyl triethoxysilane of 1.5g again, continues stirring reaction 24h down at 40 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind three (dodecyl) ammonio methacrylates and the collaborative organic surface modifying of phenyl triethoxysilane.The activation index H of gained powder is 100%.
Embodiment 10:
At first in the 100g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.The attapulgite suspension temperature is adjusted to 20 ℃, adds the benzyltriethylammoinium chloride of 0.2g, keep 20 ℃ of temperature of reaction, stirring reaction 10h.The ammonia soln that adds 2mol/L then, the pH=9 of regulation system adds the propenyl Trimethoxy silane of 1g again, continues stirring reaction 24h down at 20 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind benzyltriethylammoinium chloride and the collaborative organic surface modifying of propenyl Trimethoxy silane.The activation index H of gained powder is 95%.
Embodiment 11:
At first in the 50g deionized water, add 5g attapulgite powder, stir and make attapulgite suspension.Attapulgite suspension is heated to 50 ℃, adds the octadecyl trimethylammonium bromide of 0.25g, keep 50 ℃ of temperature of reaction, stirring reaction 10h.The ammonia soln that adds 2mol/L then, the pH=10 of regulation system adds γ-glycidyl ether oxygen propyl trimethoxy silicane of 1g again, continues stirring reaction 14h down at 50 ℃.Attapulgite suspension suction filtration after the surface modification reaction end successively respectively washs 3 times with deionized water and dehydrated alcohol.Last dry in 110 ℃ baking oven, pulverize the attapulgite powder that promptly gets behind octadecyl trimethylammonium bromide and the collaborative organic surface modifying of γ-glycidyl ether oxygen propyl trimethoxy silicane.The activation index H of gained powder is 99%.
Claims (3)
1. organic surface modifying method of attapulgite is characterized in that processing step is as follows:
(1) preparation of attapulgite suspension: the attapulgite powder is joined in the deionized water by a certain percentage, make attapulgite suspension, the attapulgite quality accounts for 5%～25% of quality;
(2) cats product is to the organic surface modifying of attapulgite: is the temperature regulation of attapulgite suspension 20～90 ℃, add cats product, the cats product quality accounts for 2～10% of attapulgite quality, stirring reaction 2～10h;
(3) silane coupling agent is to the organic surface modifying of attapulgite: after the cats product organic surface modifying finishes, pH value to 3～5 or 8～11 of regulation system, in reaction system, add silane coupling agent, the silane coupling agent quality accounts for 5～20% of attapulgite quality, at 20～90 ℃ of following stirring reaction 3～24h;
(4) organically-modified aftertreatment: with the attapulgite slurry by filtration of gained, washing, dry, pulverizing finally obtains through cats product and the equal attapulgite powder of silane coupling agent modified synergic.
2. organic surface modifying method of attapulgite according to claim 1, it is characterized in that: described cats product is the organic ammonium salt, be specially the octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, the tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, two octyl alkyl dimethyl ammonium chlorides, two nonyl alkyl dimethyl ammonium chlorides, two octyl dimethyl brometo de amonios, two nonyl dimethyl brometo de amonios, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chlorides, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, distearyl dimethyl ammonium chloride, two ten alkyl dimethyl brometo de amonios, didodecyldimethylammbromide bromide, two tetradecyl dimethyl brometo de amonios, double hexadecyl dimethyl brometo de amonio, two octadecyl dimethyl brometo de amonios, tri-n-octyl methyl ammonium chloride, three nonyl ammonio methacrylates, trioctylphosphine methyl brometo de amonio, three nonyl methyl brometo de amonios, three (ten alkyl) ammonio methacrylate, three (dodecyl) ammonio methacrylate, three (tetradecyl) ammonio methacrylate, three (hexadecyl) ammonio methacrylate, three (octadecyl) ammonio methacrylate, three (ten alkyl) methyl brometo de amonio, three (dodecyl) methyl brometo de amonio, three (tetradecyl) methyl brometo de amonio, three (hexadecyl) methyl brometo de amonio, three (octadecyl) methyl brometo de amonio, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tripropyl brometo de amonio, benzyl tributyl brometo de amonio, the phenyl trimethyl ammonium chloride, a kind of in the phenyl trimethylammonium bromide.
3. organic surface modifying method of attapulgite according to claim 1 and 2, it is characterized in that: described silane coupling agent is an organoalkoxysilane, organoalkoxysilane is a methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the isobutyl-Trimethoxy silane, the isobutyl-triethoxyl silane, the n-hexyl triethoxyl silane, the n-octyl Trimethoxy silane, the n-octyl triethoxyl silane, isooctyltrimethoxysi,ane, the iso-octyl triethoxyl silane, the dodecyl Trimethoxy silane, the n-hexadecyl Trimethoxy silane, Octadecane base Trimethoxy silane, phenyl triethoxysilane, dimethoxydiphenylsilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-dimethyl base oxethyl silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, the propenyl Trimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, α-thiopurine methyltransferase triethoxyl silane, γ-mercapto propyl group methyl dimethoxysilane, γ-mercapto propyl group methyldiethoxysilane, two-[γ-(triethoxysilicane) propyl group] disulphide, a kind of in two-[γ-(triethoxysilicane) propyl group] tetrasulfide.
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