CN101254924A - Silicane coupling agent surface grafted modified clay as well as preparation method and use thereof - Google Patents
Silicane coupling agent surface grafted modified clay as well as preparation method and use thereof Download PDFInfo
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- CN101254924A CN101254924A CNA2008101036151A CN200810103615A CN101254924A CN 101254924 A CN101254924 A CN 101254924A CN A2008101036151 A CNA2008101036151 A CN A2008101036151A CN 200810103615 A CN200810103615 A CN 200810103615A CN 101254924 A CN101254924 A CN 101254924A
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Abstract
The invention relates to the clay surface modification, in particular to modified clay with silane coupling agent grafted surface, preparation method and application thereof. The grafting modification of the silane coupling agent with a grafting amount of 0.2-5*10<-3> mol/gram clay is performed in solvent by using reactive hydroxyl group on a clay sheet layer. The inventive modified clay, in which the silane coupling agent is grafted on the clay sheet layer via the covalent bond, has strong thermostability and realizes clay functionalization while improving the clay surface lipophilicity. As the inventive clay has high thermostability and enhanced interaction with polymer, it can be used for the preparation of polymer/clay nanometer composite material to improve the clay dispersibility in the polymeric matrix for stripping and dispersing, thereby improving the performance of the composite material.
Description
Technical field
The present invention relates to the surface modification of clay, particularly silicane coupling agent surface grafted modified clay and its production and use.
Background technology
Clay is a kind of resourceful mineral, many advantages such as the commutative capacity of interlayer ion is big, interlayer charge is very high because it has, the radius-thickness ratio of lamella and specific surface area are big are widely used in during drilling well, casting, catalysis, makeup, pharmacy, coating etc. produce.Prepared polyamide 6/clay hybrid material (Polym.Prepr.1987 with nanostructure since the graduate scientist of Toyota Motor, 28 (2): 447～448), and disclose it and had since lightweight, high-strength, heat-resisting, the excellent characteristics such as barrier property, polymkeric substance/clay nano field of compounding causes investigator's very big interest.Wherein the clay of the also at most tool application prospect of research is a montmorillonite.Montmorillonite is a kind of layered silicate clay, and its basic structural unit is to be clipped between two silicon-oxy tetrahedrons the laminate structure that forms by shared Sauerstoffatom by a slice alumina octahedral, and thickness is about 1nm, length and width tens of between the hundreds of nanometer.
Its surface properties is depended in the excellent properties of clay and application thereof, so the surface modification of clay is a focus of this area research and development always.Because the hydrophilic characteristics on clay surface often needs to carry out surface modification in the practical application.For example polymkeric substance/clay nano composite material studies show that, hydrophilic clay surface is unfavorable for the intercalation of polymkeric substance, therefore need be to the clay processing that organises, improve the consistency of itself and polymkeric substance, could in polymeric matrix, disperse preparation intercal type and even exfoliated nano-composite better.The application in other field, as catalyst cupport, heavy metal and organic pollutant absorption etc. all depend on the Modulatory character and the surface modification of clay surface properties.
The method of modifying of widespread use at present is to utilize this characteristic of tradable ion is arranged between clay layer, utilize the principle of ion-exchange, with organic modifiers (cats product, be generally organic ammonium salt) insert between the clay lamella, expand its sheet interlayer spacing, improve the microenvironment of interlayer, make the surfaces externally and internally of clay be converted into hydrophobicity by wetting ability.The advantage of this method is easy to operate, and is applied widely, but its shortcoming also clearly.The polyorganosilicate thermostability of organic ammonium salt modification is relatively poor, its heat decomposition temperature is generally about 200 ℃, when melt blending prepares polymkeric substance/clay nano composite material, under the effect of high temperature high-shear, the decomposition of ammonium salt, loss can cause that the clay lamella caves in, the instability of polymer molecule degraded and nano composite material structure.Studies show that in polyorganosilicate, have 20% ammonium salt to be adsorbed on the side of clay approximately, this is major cause (J.Am.Chem.Soc.1940,62 (6): 1457～1464 that cause its thermostability relatively poor; J.Phys.Chem.1952,56 (6): 751～753.).In addition, be used for organically-modified commercialization organic ammonium salt,, also limited the functionalization of polyorganosilicate because its terminal functional group kind is limited.Because the factors such as imperfection of crystalline structure, the lateral edge of clay silicate lamella contains the hydroxyl of reactable, can carry out lateral modification, thereby overcomes the relatively poor thermostability of absorption ammonium salt in the polyorganosilicate.
Summary of the invention
A purpose of the present invention is to provide a kind of silicane coupling agent surface grafted modified clay, silane coupling agent is grafted on the clay lamella by covalent linkage, improving the clay oil loving while of surface, have stronger thermostability, can realize the functionalization of clay simultaneously.
The preparation method of the modified clay that another object of the present invention is to provide silicane coupling agent surface grafted.
A further object of the present invention provides the application of silicane coupling agent surface grafted modified clay in polymer nanocomposites.
Silicane coupling agent surface grafted modified clay of the present invention is to utilize the reactable hydroxyl on the clay lamella and the condensation reaction of silane coupling agent, is grafted with silane coupling agent on the surface of clay by covalent linkage, realizes the graft modification of silane coupling agent.The grafting amount of silane coupling agent is 0.2～5 * 10 in the modified clay
-3The moles per gram clay.
Described silane coupling agent, its general formula be (X '-R)
n-Si-X
(4-n), contain hydrolyzable radicals X and functional end-group X ', be a kind of silicoorganic compound, be widely used in the finishing of mineral filler.Silane coupling agent graft modification clay provided by the invention, when being used to prepare polymer nanocomposites such as polyolefine, polyester and polymeric amide, have thermostability preferably, can improve the interfacial interaction of polymkeric substance and clay simultaneously, help the dispersion of clay.
The preparation method of silicane coupling agent surface grafted modified clay of the present invention, at first prepare the suspension of clay in reaction solvent (dispersion agent), the solution that will contain the silane coupling agent of prehydrolysis again adds in the clay suspension, silicon hydroxyl that obtains by prehydrolysis on the silane coupling agent and the hydroxyl on the clay lamella carry out condensation reaction, obtain silicane coupling agent surface grafted modified clay; Perhaps directly silane coupling agent is added in the clay suspension, by on the silane coupling agent-hydroxyl direct reaction on X group and the clay lamella, obtain silicane coupling agent surface grafted modified clay.
The preparation method of silicane coupling agent surface grafted modified clay of the present invention may further comprise the steps:
1) preparation of clay suspension: the clay of 1～10 weight part slowly is scattered in the reaction solvent of 100～200 weight parts, stirs, forming concentration is the uniform clay suspension of 0.5～10wt%.
2) silane coupling agent being joined in the clay suspension that step 1) obtains, is 25～120 ℃ of following stirring reactions 2～48 hours in temperature; Wherein dosage of silane coupling agent is 0.2～10 * 10
-3The moles per gram clay; Or
An amount of silane coupling agent joined contain in 0～98wt% alcoholic acid aqueous solution, regulate its pH value, stir, obtain the solution that concentration is 0.2～2wt% silane coupling agent; Then this silane coupler solution slowly being joined in the clay suspension in the step 1), is 25～120 ℃ of following stirring reactions 2～48 hours in temperature; Wherein dosage of silane coupling agent is 0.2～10 * 10
-3The moles per gram clay.
3) with step 2) product that obtains filters, and removes reaction solvent, with filter cake with the cleaning solvent washing for several times, dryly and broken can obtain silicane coupling agent surface grafted modified clay.
Described stirring is selected from more than one in ultra-sonic oscillation, mechanical stirring and the induction stirring.
In step 2) in regulate pH value can to add acidic solution adjusting pH value in reaction system be 3～5, also can add basic solution adjusting pH value in reaction system is 9～10.
Clay used in the present invention is the montmorillonite type clay; Described montmorillonite type clay is selected from undressed inorganic clay, the polyorganosilicate of organic ammonium salt exchange, a kind of in the protonated clay of acidification.
The general formula of silane coupling agent used in the present invention be (X '-R)
n-Si-X
(4-n), be selected from a kind of in the following stated silane coupling agent:
(1) contains the alkyl silane of hydrolysable group, R
n-Si-X
(4-n)
(2) amino silicane coupling agent, functional end-group X ' is selected from γ-aminopropyl, N-(β-aminoethyl)-γ-aminopropyl, N, a kind of group in N '-(β-aminoethyl)-γ-aminopropyl and the anilinomethyl;
(3) alkenyl silane coupling agent, (CH
2=CH-R)
nSi-X
(4-n)
(4) epoxyalkylsilane coupling agent,
R ' is selected from-CH
2-O-(CH
2)
3,-(CH
2)
4And-(CH
2)
8In a kind of group;
(5) alkyl acryloxy silane coupling agent, (CH
2=CR '-COO-R)
nSi-X
(4-n), R ' is a kind of group in methyl or the ethyl;
(6) (HS), isocyanate group (NCO) and fluorine atom base (a kind of group F) for functional end-group X ' selected from mercapto;
In the above silane coupling agent, hydrolysable group X is selected from more than one groups in chlorine, methoxyl group, oxyethyl group, methoxy ethoxy and the acetoxyl group, and R is that the carbochain number is 1～18 alkyl, and n is 1～3.
Acid used in the present invention is mineral acid, organic acid or their mixture; Employed alkali is selected from sodium hydroxide, potassium hydroxide, a kind of in yellow soda ash and the sodium hydrogen carbonate solution.Described mineral acid is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or their mixture; Described organic acid is acetic acid, vinylformic acid, citric acid or their mixture.
Reaction solvent used in the present invention is the suspension dispersive agent at clay, is selected from water, ethanol, methyl alcohol, propyl carbinol, Virahol, acetone, benzene, toluene, dimethylbenzene and N, more than one in the dinethylformamide etc.
Cleaning solvent used in the present invention is at the solvent of excess reactant silane coupling agent, is selected from ethanol, methyl alcohol, propyl carbinol, Virahol, acetone, benzene, toluene, dimethylbenzene and N, more than one in the dinethylformamide etc.
The silicane coupling agent surface grafted modified clay of the inventive method preparation has confirmed the generation that surface grafting reacts through Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA), by this reaction success silane coupling agent is grafted on the clay lamella.
Silicane coupling agent surface grafted modified clay of the present invention, has higher thermostability, eliminated the reactive hydroxyl on the clay silicate lamella, strengthened interaction with polymkeric substance, be particularly suitable for nonpolar and the low-pole polymkeric substance, be used to prepare polymkeric substance/clay nano composite material, improve the dispersive ability of clay in polymeric matrix, reach and peel off dispersion, thereby improve performance of composites.
Description of drawings
Fig. 1. the FT-IR spectrogram of the clay of the montmorillonite clay of the embodiment of the invention 1 and the graft modification of dodecyl Trimethoxy silane; Wherein: A: the montmorillonite clay; B: the clay of dodecyl Trimethoxy silane graft modification.
Fig. 2. the TGA figure of the clay of the montmorillonite clay of the embodiment of the invention 1 and the graft modification of dodecyl Trimethoxy silane; Wherein: A: the montmorillonite clay; B: the clay of dodecyl Trimethoxy silane graft modification.
Fig. 3. the TGA figure of the polyorganosilicate of the polyorganosilicate of the cetyl trimethylammonium bromide intercalation of the embodiment of the invention 7 and the graft modification of dodecyl Trimethoxy silane; Wherein: A: the polyorganosilicate of cetyl trimethylammonium bromide intercalation; B: the polyorganosilicate of dodecyl Trimethoxy silane graft modification.
Fig. 4. the transmission electron microscope photo of the polyethylene nano composite material of the polyorganosilicate of the cetyl trimethylammonium bromide exchange of the embodiment of the invention 12 and the polyorganosilicate of dodecyl Trimethoxy silane graft modification; Wherein: A: the polyorganosilicate of polyethylene/cetyl trimethylammonium bromide exchange; B: the polyorganosilicate of polyethylene/dodecyl Trimethoxy silane graft modification.
Embodiment
Below in conjunction with embodiment technical characterictic of the present invention is described, need to prove that these just part descriptions for example do not constitute the restriction to content of the present invention.
Embodiment 1
The inorganic clay of the undressed montmorillonite of 10g is scattered in the 200mL toluene, stirs, and waits to be uniformly dispersed, and forms steady suspension.5mL dodecyl Trimethoxy silane is slowly splashed in the suspension, and mechanical stirring is warming up to 110 ℃, back flow reaction 24 hours.Reaction finishes back B suction filtration, and with filter cake with toluene wash some times, 80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting dodecyl Trimethoxy silane.The grafting amount that records the dodecyl Trimethoxy silane on the modified clay of surface grafting dodecyl Trimethoxy silane with TGA is 0.26 * 10
-3The moles per gram clay.
Embodiment 2
Measure the 80mL dehydrated alcohol, the 20mL deionized water is mixed in the beaker magnetic agitation; Add Glacial acetic acid, regulate pH between 4～5, add 10mL dodecyl Trimethoxy silane, room temperature continues to stir 1 hour, obtains solution of silane.
The inorganic clay of the undressed montmorillonite of 10g is scattered in the mixed solvent of 90mL propyl carbinol and 10mL deionized water composition, stir, wait to be uniformly dispersed, form steady suspension, the solution of silane that aforesaid method is obtained is added dropwise in the clay suspension, is warming up to 78 ℃, add Glacial acetic acid, regulate pH between 4～5, mechanical stirring was reacted 24 hours.Reaction finishes back B suction filtration, and filter cake is washed some times with dehydrated alcohol/deionized water mixed solvent, is 6～7 until filtrate pH value.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting dodecyl Trimethoxy silane.The grafting amount that records the dodecyl Trimethoxy silane on the modified clay of surface grafting dodecyl Trimethoxy silane with TGA is 2.4 * 10
-3The moles per gram clay.
Embodiment 3
Measure the 180mL dehydrated alcohol, the 20mL deionized water is mixed in the beaker mechanical stirring; Add Glacial acetic acid, regulate pH between 4～5, add 5mL dodecyl Trimethoxy silane, room temperature continues to stir 1 hour, obtains solution of silane.
The inorganic clay of the undressed montmorillonite of 10g is scattered in the mixed solvent of 180mL dehydrated alcohol and 20mL deionized water composition, stir, wait to be uniformly dispersed, form steady suspension, the solution of silane that aforesaid method is obtained is added dropwise in the clay suspension, is warming up to 78 ℃, add sodium hydroxide solution, regulate pH between 9～10, mechanical stirring was reacted 24 hours.Reaction finishes back B suction filtration, and filter cake is washed some times with dehydrated alcohol/deionized water mixed solvent, is 6～7 until filtrate pH value.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting dodecyl Trimethoxy silane.The grafting amount that records the dodecyl Trimethoxy silane on the modified clay of surface grafting dodecyl Trimethoxy silane with TGA is 1.1 * 10
-3The moles per gram clay.
Embodiment 4
Measure the 70mL dehydrated alcohol, the 30mL deionized water is mixed in the beaker, the hertzian wave vibration; Add the 3.2mL γ-An Bingjisanyiyangjiguiwan, room temperature continues to stir 1 hour, obtains solution of silane.
The inorganic clay of the undressed montmorillonite of 10g is scattered in the mixed solvent of 90mL dehydrated alcohol and 10mL deionized water composition, stir, wait to be uniformly dispersed, form steady suspension, the solution of silane that aforesaid method is obtained is added dropwise in the clay suspension, be warming up to 78 ℃, mechanical stirring was reacted 24 hours.Reaction finishes back B suction filtration, and filter cake is washed some times with dehydrated alcohol/deionized water mixed solvent.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting γ-An Bingjisanyiyangjiguiwan.The grafting amount that records the γ-An Bingjisanyiyangjiguiwan on the modified clay of surface grafting γ-An Bingjisanyiyangjiguiwan with TGA is 0.9 * 10
-3The moles per gram clay.
Embodiment 5
The inorganic clay of the undressed montmorillonite of 5g is scattered in the 50mL anhydrous propanone, stirs, and waits to be uniformly dispersed, and forms steady suspension, adds the 5mL trimethylchlorosilane, and mechanical stirring is warming up to 50, with nitrogen protection, reacts 24 hours.Reaction finishes back B suction filtration, and with filter cake washing with acetone some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting trimethylchlorosilane.The grafting amount that records the trimethylchlorosilane on the modified clay of surface grafting trimethylchlorosilane with TGA is 0.6 * 10
-3The moles per gram clay.
Embodiment 6
Measure the 100mL deionized water, add Glacial acetic acid, regulate pH between 4～5, add 7.2mL γ-(methacryloxypropyl) propyl trimethoxy silicane, stirring at room 1 hour obtains solution of silane.
The acidifying montmorillonite clay of 10g hcl acidifying is scattered in the 100mL deionized water, stir, wait to be uniformly dispersed, form steady suspension, the solution of silane that aforesaid method is obtained is added dropwise in the clay suspension, is warming up to 80 ℃, add Glacial acetic acid, regulate pH between 4～5, mechanical stirring was reacted 24 hours.Reaction finishes back B suction filtration, and with filter cake deionized water wash some times, is 6～7 until filtrate pH value.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane.The grafting amount that records γ-(methacryloxypropyl) propyl trimethoxy silicane on the modified clay of surface grafting γ-(methacryloxypropyl) propyl trimethoxy silicane with TGA is 1.9 * 10
-3The moles per gram clay.
Embodiment 7
The polyorganosilicate of 10g cetyl trimethylammonium bromide intercalation is scattered in the 200mL dimethylbenzene, stirs, and waits to be uniformly dispersed, and forms stable clear solution.5mL dodecyl Trimethoxy silane is slowly splashed in the solution, and mechanical stirring is warming up to 110 ℃, reacts 24 hours.Reaction finishes back B suction filtration, and with filter cake with dimethylbenzene, washing with acetone some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modification polyorganosilicate of surface grafting dodecyl Trimethoxy silane.The grafting amount that records the dodecyl Trimethoxy silane on the modification polyorganosilicate of surface grafting dodecyl Trimethoxy silane with TGA is 0.22 * 10
-3The moles per gram clay.
Embodiment 8
The acidifying montmorillonite clay of 5g hcl acidifying is scattered in 100mL N, in the dinethylformamide, stir, wait to be uniformly dispersed, form steady suspension, 5mL γ-(methacryloxypropyl) propyl-dimethyl methoxy silane is slowly splashed in the solution mechanical stirring, be warming up to 110 ℃, reacted 24 hours.Reaction finishes back B suction filtration, and with filter cake N, dinethylformamide, washing with acetone some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting γ-(methacryloxypropyl) propyl-dimethyl methoxy silane.The grafting amount that records γ-(methacryloxypropyl) propyl-dimethyl methoxy silane on the modified clay of surface grafting γ-(methacryloxypropyl) propyl-dimethyl methoxy silane with TGA is 2.1 * 10
-3The moles per gram clay.
Embodiment 9
The polyorganosilicate of the two octadecyl dimethyl brometo de amonio intercalations of 5g is scattered in the 200mL benzene, stirs, and waits to be uniformly dispersed, and forms stable clear solution.The 2mL glycidoxy-propyltrimethoxy silane is slowly splashed in the solution, and mechanical stirring is warming up to 80 ℃, reacts 24 hours.Reaction finishes back B suction filtration, and with filter cake with benzene, washing with acetone some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting glycidoxy-propyltrimethoxy silane.The grafting amount that records the glycidoxy-propyltrimethoxy silane on the modified clay of surface grafting glycidoxy-propyltrimethoxy silane with TGA is 0.6 * 10
-3The moles per gram clay.
Embodiment 10
The inorganic montmorillonite clay of 5g is scattered in the 100mL ethanol, stirs, and waits to be uniformly dispersed, and forms steady suspension, adds the 5mL gamma-mercaptopropyltriethoxysilane, and mechanical stirring is warming up to 50, reacts 24 hours.Reaction finishes back B suction filtration, and with filter cake washing with alcohol some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting gamma-mercaptopropyltriethoxysilane.The grafting amount that records the gamma-mercaptopropyltriethoxysilane on the modified clay of surface grafting gamma-mercaptopropyltriethoxysilane with TGA is 1.7 * 10
-3The moles per gram clay.
Embodiment 11
The inorganic montmorillonite clay of 10g is scattered in the 500mL toluene, stirs, and waits to be uniformly dispersed, and forms steady suspension, adds 2mL isocyanic ester propyl-triethoxysilicane, and mechanical stirring is warming up to 110, reacts 24 hours.Reaction finishes back B suction filtration, and with filter cake washing with alcohol some times.80 ℃ of dryings 24 hours are ground and are powder, obtain the modified clay of surface grafting isocyanic ester propyl-triethoxysilicane.The grafting amount that records the isocyanic ester propyl-triethoxysilicane on the modified clay of surface grafting isocyanic ester propyl-triethoxysilicane with TGA is 0.36 * 10
-3The moles per gram clay.
Embodiment 12
Adopt the modification polyorganosilicate of the surface grafting dodecyl Trimethoxy silane of the embodiment of the invention 7 preparations, and without the polyorganosilicate of the cetyltrimethyl ammonium salt intercalation of graft modification, prepared polyethylene/clay nano composite material with following melt-blending process: the new national standard PE-M-13D022 type of 100 weight parts (the mark 1I2A of old-national type) new LDPE (film grade) is pre-mixed with above-mentioned two kinds of polyorganosilicates of 0.5～10 weight part respectively, go up banburying blend 10 minutes at HAAKE torque rheometer (German HAAKE company), rotating speed is 50rpm, and temperature is 190 ℃.Adopt the modification polyorganosilicate of surface grafting dodecyl Trimethoxy silane, owing to eliminated the reactive hydroxyl on the clay silicate lamella, the clay lamella is easy to peel off, and can obtain polyethylene/clay nano composite material; And there is reactive hydroxyl without the polyorganosilicate of the cetyltrimethyl ammonium salt intercalation of graft modification in employing owing on the clay silicate lamella, and relatively poor with poly affinity, the clay lamella is difficult to peel off, and can only obtain polyethylene/clay micron matrix material.
Claims (10)
1. silicane coupling agent surface grafted modified clay, it is characterized in that: utilize the reactable hydroxyl on the clay lamella and the condensation reaction of silane coupling agent, surface at clay is grafted with silane coupling agent by covalent linkage, and wherein the grafting amount of silane coupling agent is 0.2～5 * 10
-3The moles per gram clay.
2. silicane coupling agent surface grafted modified clay according to claim 1 is characterized in that: described clay is the montmorillonite type clay.
3. silicane coupling agent surface grafted modified clay according to claim 2 is characterized in that: described montmorillonite type clay is selected from undressed inorganic clay, the polyorganosilicate of organic ammonium salt exchange and a kind of in the protonated clay of acidification.
4. silicane coupling agent surface grafted modified clay according to claim 1 is characterized in that: the general formula of described silane coupling agent for (X '-R)
n-Si-X
(4-n), be selected from a kind of in the following stated silane coupling agent:
(1) contains the alkyl silane of hydrolysable group, R
n-Si-X
(4-n)
(2) amino silicane coupling agent, functional end-group X ' is selected from γ-aminopropyl, N-(β-aminoethyl)-γ-aminopropyl, N, a kind of group in N '-(β-aminoethyl)-γ-aminopropyl and the anilinomethyl;
(3) alkenyl silane coupling agent, (CH
2=CH-R)
nSi-X
(4-n)
(4) epoxyalkylsilane coupling agent,
R ' is selected from-CH
2-O-(CH
2)
3,-(CH
2)
4And-(CH
2)
8In a kind of group;
(5) alkyl acryloxy silane coupling agent, (CH
2=CR '-COO-R)
nSi-X
(4-n), R ' is a kind of group in methyl or the ethyl;
(6) a kind of group in functional end-group X ' selected from mercapto, isocyanate group and the fluorine atom base;
In the above silane coupling agent, hydrolysable group X is selected from more than one groups in chlorine, methoxyl group, oxyethyl group, methoxy ethoxy and the acetoxyl group, and R is that the carbochain number is 1～18 alkyl, and n is 1～3.
5. preparation method according to each described silicane coupling agent surface grafted modified clay of claim 1～4 is characterized in that this method may further comprise the steps:
1) clay with 1～10 weight part slowly is scattered in the reaction solvent of 100～200 weight parts, stirs, and forms uniform clay suspension;
2) silane coupling agent being joined in the clay suspension that step 1) obtains, is 25～120 ℃ of following stirring reactions in temperature; Wherein dosage of silane coupling agent is 0.2～10 * 10
-3The moles per gram clay; Or
Silane coupling agent joined contain in 0～98wt% alcoholic acid aqueous solution, regulating its pH value with acid is 3～5 or to regulate its pH value with alkali be 9～10; Stirring obtains the solution of silane coupling agent; Then this silane coupler solution slowly being joined in the clay suspension in the step 1), is 25～120 ℃ of following stirring reactions in temperature; Wherein dosage of silane coupling agent is 0.2～10 * 10
-3The moles per gram clay;
3) with step 2) product that obtains filters, and removes reaction solvent, and with the filter cake solvent wash, drying obtains silicane coupling agent surface grafted modified clay.
6. method according to claim 5 is characterized in that: step 2) described be that time of 25～120 ℃ of following stirring reactions is 2～48 hours in temperature.
7. method according to claim 5 is characterized in that: described acid is mineral acid, organic acid or their mixture;
Described alkali is selected from sodium hydroxide, potassium hydroxide, a kind of in yellow soda ash and the sodium hydrogen carbonate solution.
8. method according to claim 7 is characterized in that: described mineral acid is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or their mixture; Described organic acid is acetic acid, vinylformic acid, citric acid or their mixture.
9. method according to claim 5 is characterized in that: described reaction solvent is selected from water, ethanol, methyl alcohol, propyl carbinol, Virahol, acetone, benzene, toluene, dimethylbenzene and N, more than one in the dinethylformamide;
Described washer solvent is selected from ethanol, methyl alcohol, propyl carbinol, Virahol, acetone, benzene, toluene, dimethylbenzene and N, more than one in the dinethylformamide.
10. purposes according to each described silicane coupling agent surface grafted modified clay of claim 1～4, it is characterized in that: described silicane coupling agent surface grafted modified clay is used to prepare polymkeric substance/clay nano composite material, improve the dispersive ability of clay in polymeric matrix, reach and peel off dispersion, thereby improve performance of composites.
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