CN108239424A - A kind of transparent silane-modified nano imvite dispersion liquid and its preparation method and application - Google Patents
A kind of transparent silane-modified nano imvite dispersion liquid and its preparation method and application Download PDFInfo
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- CN108239424A CN108239424A CN201611228251.0A CN201611228251A CN108239424A CN 108239424 A CN108239424 A CN 108239424A CN 201611228251 A CN201611228251 A CN 201611228251A CN 108239424 A CN108239424 A CN 108239424A
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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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- 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
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Abstract
The present invention provides a kind of transparent silane-modified nano imvite dispersion liquid and its preparation method and application, and the preparation method includes the following steps：1) prepared by hydrolyzed silane solution：Solution of silane with water is mixed, prepares the hydrolyzed silane solution；2) under stiring, nano imvite is dispersed in water to form transparent dispersion；3) hydrolyzed silane solution that step 1) is prepared is added in the dispersion that step 2) is prepared, and azeotropic solvent is added portionwise, distill out the azeotropic liquid of organic solvent, water and azeotropic solvent；When no azeotropic liquid distillates, optionally, remaining part or all of solvent is removed, obtains paste；4) solution of silane is added dropwise in the paste that step 3) is prepared, that is, transparent silane-modified nano imvite dispersion liquid is prepared.The silane-modified nano imvite dispersion liquid can be applied in optical material, such as the material is applied in LED encapsulation material.
Description
Technical field
The invention belongs to silane-modified nano imvite technical fields, and in particular to a kind of transparent silane-modified to receive
Rice montmorillonite dispersions and its preparation method and application.
Background technology
Montmorillonite (montmorillonite) is one kind of clay, has lamellar aluminosilicate structure.Montmorillonite has layer
Between the features such as commutative capacity of cation is big, interlayer charge is high, the radius-thickness ratio and large specific surface area of lamella, polymer modification,
Cosmetics, pharmacy, catalysis, coating etc. have a wide range of applications.
The structure cell of montmorillonite is made of one layer of alumina octahedral of entrainment among two layers of oxygen-octahedron, and piece interlamellar spacing is about
1nm.The trivalent aluminium in tetravalence silicon and alumina octahedral in montmorillonite structure cell in oxygen-octahedron is respectively by low valence metal ion
Such as trivalent aluminium ion and divalent magnesium ionic portions isomorphous substitution, and sheet surfaces is made to carry negative electrical charge.These superfluous negative electrical charges
It is balanced by the tradable alkali metal ion that adsorbs or alkaline-earth metal ions, the montmorillonites such as sodium base, calcium base can be formed.
Unmodified montmorillonite has stronger hydrophily, but to the compatibility of organic solvent, organic molecule or polymer
It is poor with compatibility.Organic modification montmonrillonite, which is one, improves its hydrophilic and hydrophobic, enhances itself and organic matter compatibility, and improving it should
With the important means of performance.There are two types of the common organically-modified methods of montmorillonite：One kind is commutative using having between cheating engaging layer
This cationic characteristic, ion-exchange reactions is carried out using organic cation and is modified (organic cation intercalation modifying)；
It is another then be by montmorillonite surface can reactive group, such as：Si-OH, Al-OH etc., by organic modifiers with covalent bond
Grafting mode is modified montmorillonite (grafting coupling modifier).
Chinese patent application No. is 201110298322.5 discloses a kind of aminosilane coupling agent modifying nanoclay,
It is using amino silicane coupling agent as modifying agent, and modified clay is dispersed among benzene, toluene, acetonitrile, tetrahydrofuran, hexamethylene
In the organic solvents such as alkane, ether.Chinese patent application No. is 200710080074.0 discloses a kind of amino silicane coupling agent
Modified inorganic clay, it for less than 18 microns of montmorillonite is raw material to use size, using amino silicane coupling agent as modifying agent,
But obtained modified product is opaque under visible light.Zhao Chungui etc. uses Chi orosilane-modified Montmorillonites, and silane is successfully
It has been intercalation into piece interlayer (Chemical Journal of Chinese Universities, 2003,24 (5) of montmorillonite:928-931).Application No. is
200810103615.1 Chinese patent discloses a kind of silane coupler modified inorganic clay, is by surface grafting silicon
The mode of alkane coupling agent, is modified it, and obtained clay can be used for preparing composite nano polymer/clay material.On
The method for only reporting modified montmorillonoid in the prior art and obtained modified montmorillonoid are stated, does not refer to modified illiteracy
The transparency of de- soil dispersion liquid.
It is well known that compared with the montmorillonite of large-size, the montmorillonite of nano-scale as polymer composite parts, urge
Agent carrier, pharmaceutical carrier etc. have many advantages.To the organically-modified also it has been reported that can continue to use substantially of nano imvite
The cation-intercalated modification of machine and the method for being grafted coupling modifier.Even if organically-modified to the progress of hydrophilic nano imvite,
If not control condition, in media environment variation and modifying agent reaction process, it is easy to reunite, it is impossible to be formed in organic
There is the modified nano montmorillonite of good dispersion in medium.Wherein, the phenomenon that one apparent be exactly modified montmorillonite not
Transparent dispersion can be formed in organic media.Chinese patent application No. is 201080037575.0 discloses one kind and changes
Property clay dispersion liquid preparation method, the method is modified by tetraphenylphosphoniphenolate, so as to be prepared one kind with water electrode
Property solvent dispersing liquid as main component.
At present, for silane-modified montmorillonite, dispersion liquid is all often opaque, and there are no transparent is free of
The organic media dispersion of water is reported that opaque montmorillonite dispersions, which are applied to range and performance, serious limit
System.
Invention content
In order to overcome deficiency of the prior art, an object of the present invention is to provide a kind of transparent silane-modified receive
Rice montmorillonite dispersions.By the selection to silane modifier and the control of reaction condition, transparent silane can be prepared
Modified nano imvite dispersion liquid can be overcome existing for the silane-modified montmorillonite dispersions reported in the prior art not
Transparent problem.
The second object of the present invention is to provide a kind of preparation method of above-mentioned silane-modified nano imvite dispersion liquid.Institute
It states in preparation method, selects suitable silane modifier, in addition to other than montmorillonite grafting coupling, may be incorporated into a variety of reactive groups
Group, so that the transparent silane-modified nano imvite dispersion liquid being prepared has different hydrophilicity and hydrophobicities.
The third object of the present invention is to provide the application of above-mentioned silane-modified nano imvite dispersion liquid, can conduct
The added material of packaging material as the auxiliary agent of transparent material, can also increase the intensity of product, barrier properties for gases, adjust material
Expect the heat-resisting performances such as water-fast of refractive index, the anti-flammability of reinforcing material, the flatness of material surface, material.
The present invention seeks to what is be achieved through the following technical solutions：
A kind of transparent silane-modified nano imvite dispersion liquid, composition contain：
a：Silane-modified nano imvite, weight percent are 0.01~30wt%, preferably 0.1~20wt%；
b：Decentralized medium, weight percent are 70~99.99wt%, preferably 80~99.9wt%；
Wherein, the decentralized medium includes b-1) silicone fluid medium；The b-1) silicone fluid medium be silicon
Alkane and its partial hydrolysis condensation product, the weight percent for accounting for decentralized medium are 30~100wt%；
Wherein, the sum of weight percent of each component is 100wt% in dispersion liquid.
According to the present invention, b-2 is further included in the decentralized medium) organic solvent medium and b-3) azeotropic solvent medium；Institute
The b-2 stated) organic solvent medium account for decentralized medium weight percent be 0~65wt%；The b-3) azeotropic solvent medium
The weight percent for accounting for decentralized medium is 0~5wt%.
In the present invention, so-called " transparent " refers to the 1 micron thick liquid of the silane-modified nano imvite dispersion liquid
Film transmitance >=50% (being measured under 200-800nm wavelength, observe the transmitance under 630nm wavelength) of body.
According to the present invention, the grain size of the nano imvite is between 200~400 mesh.
Preferably, the nano imvite is water nano montmorillonite.
Preferably, the water nano montmorillonite is selected from sodium base nano imvite, calcium base nano imvite, Sodium/Calcium base
Nano imvite or magnesium-base nano montmorillonite.
It is further preferred that the water nano montmorillonite is selected from sodium base nano imvite or Sodium/Calcium base nano imvite.
According to the present invention, the silane is selected from DfOne or more of mixture or selected from DfOne or more of
With Tf、Mf, one or more of M mixture, the Df、Tf、Mf, M have following molecular formula：
Wherein,
Df、MfIt is identical or different with the R in M, it is independently from each other C1-6Alkyl, C2-6Alkenyl, C6-14Aryl, C3-10Alkane
Base oxygroup (methyl) is acrylate-based and C3-10Alkyl oxy epoxy C3-10Alkyl, when containing more than two R, each R it is identical or
It is different；
Df、Tf、MfIt is identical or different with the R' in M, it is independently from each other H, C1-6Alkyl, when containing more than two R'
When, each R' is identical or different；
Df、TfAnd MfIn RfIt is identical or different, it is independently from each other-(CxH2x)-[NH-(CH2)m]n-NH2Or-
(CyH2y)-NH-(CzH2z)-[CHO(CH3)CH2]k-NH2, wherein, x is the integer between 1 to 11, and n is the integer between 0 to 5,
M is the integer between 1 to 6, and y, z are the integer between 1 to 6, and k is the integer between 1 to 5.
Preferably, R is selected from methyl, ethyl, isopropyl, propyl, butyl, isobutyl group, vinyl, acrylic, phenyl, the third oxygen
Base is acrylate-based, propoxy methyl is acrylate-based and propoxyl group glycidyl, and when containing more than two R, each R is identical
It is or different.
Preferably, R' is selected from H, methyl, ethyl, isopropyl, propyl, butyl and isobutyl group, when containing more than two R',
Each R' is identical or different.
Preferably, RfSelected from-(CyH2y)-NH-(CzH2z)-[CHO(CH3)CH2]k-NH2Or-(CH2)x[NH(CH2)m]nNH2,
Wherein, y, z are the integer between 2 to 4, and k is the integer between 1 to 3, and x 1,3,4,11, n are integer between 0 to 3, and m is
2、6。
It is further preferred that RfSelected from-CH2CH2CH2NHCH(CH3)CH2[CHO(CH3)CH2]2NH2Or-CH2CH(CH3)
CH2NHCH2CH2NH2One or both of.
Most preferably, the silane is selected from N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane or N- β-(ammonia second
Base) one or both of-γ-aminopropyltriethoxy dimethoxysilane mixture or selected from N- (2- amino-ethyls)-isobutyl
One or both of ylmethyl dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and 3- ammonia
The mixing of one or both of propyl-dimethyl Ethoxysilane, N- (2- amino-ethyls)-TSL 8330
Object.
According to the present invention, D in the silanefWeight percent >=30wt% (preferably, weight percent >=
50wt%), weight percent≤10wt% (preferably, weight percent≤5wt%) of M.
According to the present invention, the b-2) organic solvent medium is selected from methanol, ethyl alcohol, isopropanol, just normal propyl alcohol, (different) fourth
Alcohol, acetone, tetrahydrofuran, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol, glycol monoethyl ether, second two
One or more of diethylene glycol dimethyl ether, acetonitrile, ethyl acetate, aniline, methyl ethyl ketone, pyridine, acetic acid.
According to the present invention, the b-3) azeotropic solvent medium be selected from ethyl alcohol, just (different) propyl alcohol, just (different) butanol, ether,
Chloroform, dichloroethanes, benzene,toluene,xylene, methyl phenyl ethers anisole, phenetole, dioxane, ethyl acetate, tetrahydrofuran, pyridine, first
One kind in acid, acetic acid.
The present invention also provides the preparation method of above-mentioned silane-modified nano imvite dispersion liquid, the preparation method includes
Following steps：
1) prepared by hydrolyzed silane solution：Solution of silane with water is mixed, prepares the hydrolyzed silane solution；
2) under stiring, nano imvite is dispersed in water to form transparent dispersion；
3) hydrolyzed silane solution that step 1) is prepared is added in the dispersion that step 2) is prepared, and in batches
Azeotropic solvent is added in, distills out the azeotropic liquid of organic solvent, water and azeotropic solvent；When no azeotropic liquid distillates, optionally, remove
Remaining part or all of solvent, obtains paste；
4) solution of silane is added dropwise in the paste that step 3) is prepared, that is, transparent silane is prepared and changes
The nano imvite dispersion liquid of property.
According to the present invention, in step 1) and step 4), the solution of silane is the mixed liquor of silane and organic solvent,
Wherein, the mass concentration of silane is 1~100wt% in solution of silane.
According to the present invention, the organic solvent in the solution of silane is selected from methanol, ethyl alcohol, isopropanol, just normal propyl alcohol, (different)
Butanol, acetone, tetrahydrofuran, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol, glycol monoethyl ether, second
One or more of glycol dimethyl ether, acetonitrile, ethyl acetate, aniline, methyl ethyl ketone, pyridine, acetic acid.
In the present invention, the contact area for being added to increase silane and water of organic solvent, has in the solution of silane
Conducive to the hydrolysis of silane.
According to the present invention, in step 1), the preparation condition of the hydrolyzed silane solution is：The solution of silane is mixed with water
After conjunction, 0.5~10h is stirred at 0~80 DEG C, it is preferable that 0.5~6h is stirred at 10~50 DEG C.
According to the present invention, in step 1), the molar ratio of the silane and water is 1:0.1~25, preferably 1:0.5~
20；Further preferably 1:0.5~6.
According to the present invention, in step 2), the nano imvite is preferably grain size between 200~400 mesh.
According to the present invention, the cation exchange capacity of the nano imvite is 50~300mmol/100g, it is preferable that institute
The cation exchange capacity for stating nano imvite is 80~150mmol/100g.
According to the present invention, in step 2), the nano imvite be dispersed in water to be formed mass concentration for 0.01~
The transparent dispersion system of 50wt%.
Preferably, the nano imvite is dispersed in water the transparent dispersion to form that mass concentration is 0.1~30wt%
System.
According to the present invention, in step 3), the hydrolyzed silane solution is added dropwise in the dispersion, is covered
The mass ratio of de- soil and silane is 1:0.1~30 (preferably 1:1~20) stirring 0.5~for 24 hours is (preferably, and at 0~80 DEG C
Ground stirs 0.5~12h at 10~50 DEG C), and azeotropic solvent is added portionwise, gradually heat up, distill out organic solvent, water with
The azeotropic liquid of azeotropic solvent, until when being supplemented azeotropic solvent distillation, no azeotropic liquid distillates.
According to the present invention, in step 3), when no azeotropic liquid distillates, optionally, removed by distillation or rotary evaporation
Remaining part or all of solvent, you can paste is prepared.
According to the present invention, in step 3), the azeotropic solvent is selected from ethyl alcohol, just (different) propyl alcohol, just (different) butanol, second
Ether, chloroform, dichloroethanes, benzene,toluene,xylene, methyl phenyl ethers anisole, phenetole, dioxane, ethyl acetate, tetrahydrofuran, pyrrole
One kind in pyridine, formic acid, acetic acid.
According to the present invention, in step 4), carry out lower solution of silane being added dropwise to step in stirring and ultrasound condition
3) in the paste being prepared, that is, transparent silane-modified nano imvite dispersion liquid is prepared.
According to the present invention, in step 4), modified nanometer in the transparent silane-modified montmorillonite dispersions
The mass concentration of montmorillonite is 0.01~30wt%, preferably 1~20wt%
According to the present invention, in step 4), silane and its portion in the transparent silane-modified montmorillonite dispersions
It is 70~99.99wt%, preferably 80~99wt% to divide the mass concentration of hydrolysis condensation product and organic solvent medium.
The present invention also provides the applications of above-mentioned silane-modified nano imvite dispersion liquid, can be as packaging material
Additive as the auxiliary agent of transparent material, can also increase the intensity of product, barrier properties for gases, adjustment Refractive Index of Material, enhance
The heat-resisting performances such as water-fast of the anti-flammability of material, the flatness of material surface, material.
Preferably, the silane-modified nano imvite dispersion liquid can be applied in optical material, such as should
Material is applied in LED encapsulation material.
Beneficial effects of the present invention：
It is described transparent silane-modified 1. the present invention provides a kind of transparent silane-modified nano imvite dispersion liquid
Nano imvite dispersion liquid can overcome the opacity of nano imvite organic dispersions or aqueous dispersions and organic substance phase
The problems such as capacitive is poor, while the reactable functional group in silane structure is introduced into nano imvite surface.
2. the present invention also provides the preparation method of above-mentioned dispersion liquid, the preparation method can obtain a kind of transparent be free of
The organic media dispersion of water, and the reaction process is simple, operation is easy, production efficiency is high, is suitble to industrialization extensive
Production.
3. the present invention provides the application of above-mentioned nano imvite dispersion liquid again, the dispersion liquid is applicable to saturating to material
The every field that lightness requires, such as transparent dispersion liquid can be applied in optical material, especially LED light package material
The fields such as material, coating, environmental protection.
Description of the drawings
Fig. 1 is the transparent amino silane modified nano imvite dispersion liquid that embodiment 5 is prepared.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after recorded content of the invention has been read, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
Aqueous montmorillonite in following embodiments is selected from sodium base nano imvite, calcium base nano imvite, Sodium/Calcium base nanometer
Montmorillonite or magnesium-base nano montmorillonite, it is preferable that the aqueous montmorillonite is selected from sodium base nano imvite or Sodium/Calcium base nanometer is covered
De- soil.
Embodiment 1
The aqueous montmorillonites of 1.0g (clay) are added in 500ml deionized waters while stirring, 0.2wt% montmorillonites are made
Aqueous solution.Measure N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane (molal weight 220g/mol) 0.15g, room
15ml methanol is added dropwise under warm stirring condition to form solution of silane, 0.0012g deionized waters are added dropwise again after mixing, are stirred at room temperature
2h.By N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane after hydrolysis, it is added dropwise to 0.2wt% under stirring at room temperature
In montmorillonite aqueous solution, 1h is stirred, then starts to distill, temperature is slowly raised to be added dropwise 2000ml first while stirring in the process
Benzene does not have fraction in temperature-rise period until temperature reaches 115 DEG C, and distillation obtains removal solvent until without fraction (about 4-5h)
Then remaining solvent by revolving is all removed, obtains silane-modified nanometer by the sample after (toluene, methanol, water) again
Montmorillonite paste.Weigh N- (2- amino-ethyls)-isobutyl group that the silane-modified nano imvite pastes of 0.2g are dissolved in 2ml
(N- (2- amino-ethyls)-isobutyl methyl diformazan in the mixed solution in the mixed solution of methyl dimethoxysilane and DMF
50%) concentration expressed in percentage by volume of oxysilane is, first uniformly disperses into graininess, using ultrasound under conditions of stirring
40min obtains the dispersion liquid containing nano imvite silane-modified 10wt%.The dispersion liquid is transparent uniform liquid.
Embodiment 2
The aqueous montmorillonites of 1.0g (clay) are added in 100ml deionized waters while stirring, 1wt% montmorillonite water is made
Solution.N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane (molal weight 220g/mol) 6g is measured, is stirred at room temperature
Under the conditions of be added dropwise 6ml ethyl alcohol to form solution of silane, 0.98g deionized waters are added dropwise again after mixing, 2h is stirred at room temperature.After hydrolyzing
N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane, be added dropwise to 0.2wt% montmorillonite aqueous solutions under stirring at room temperature
In, 1h is stirred, then starts to distill, temperature is slowly raised to be added dropwise 220ml toluene while stirring in the process, does not have in temperature-rise period
There is fraction until temperature reaches 115 DEG C, distillation is until without fraction (about 4-5h), after obtaining removal solvent (toluene, ethyl alcohol, water)
Sample, then again by revolving by remaining solvent all remove, obtain silane-modified nano imvite paste.It weighs
Nano imvite paste silane-modified 0.1g is dissolved in N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane of 10ml
With (the volume of N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane in the mixed solution in the mixed solution of DMSO
Percentage concentration is 5%), graininess first to be uniformly dispersed under conditions of stirring, is obtained using ultrasonic 40min containing 1wt%
The dispersion liquid of silane-modified nano imvite.The dispersion liquid is transparent uniform liquid.
Embodiment 3
The aqueous montmorillonites of 1.0g (clay) are added in 10ml deionized waters while stirring, 10wt% montmorillonite water is made
Solution.Measure N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane (molal weight 220g/mol) 1g, N- (2- ammonia
Base ethyl)-TSL 8330 (molal weight 204g/mol) 1g, 15ml methanol is added dropwise under the conditions of being stirred at room temperature
To form solution of silane, 6g deionized waters are added dropwise again after mixing, 2h is stirred at room temperature.By the N- (2- amino-ethyls) after hydrolysis-different
Butyl methyl dimethoxysilane and N- (2- amino-ethyls)-TSL 8330, are added dropwise under stirring at room temperature
In 10wt% montmorillonite aqueous solutions, 1h is stirred, then starts to distill, temperature is slowly raised to be added dropwise 70ml while stirring in the process
Dichloroethanes does not have fraction in temperature-rise period until temperature reaches 110 DEG C, and distillation is gone until without fraction (about 4-5h)
Except the sample after solvent (dichloroethanes, methanol, water), then remaining solvent is all removed by revolving again, obtains silane
Modified nano imvite paste.Weigh N- (the 2- amino that the silane-modified nano imvite pastes of 0.1g are dissolved in 0.4ml
Ethyl)-isobutyl methyl dimethoxysilane and N- (2- amino-ethyls)-TSL 8330 mixed solution in
(in the mixed solution, N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane and N- (2- amino-ethyls)-aminopropan
The volume ratio of base trimethoxy silane is 1:1) graininess first, is uniformly dispersed under conditions of stirring, using ultrasonic 40min
Obtain the dispersion liquid containing nano imvite silane-modified 25wt%.The dispersion liquid is transparent uniform liquid.
Embodiment 4
The aqueous montmorillonites of 1.0g (clay) are added in 5ml deionized waters while stirring, 20wt% montmorillonite water is made
Solution.Measure N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane (molal weight 220g/mol) 6g, N- (2- ammonia
Base ethyl)-TSL 8330 (molal weight 204g/mol) 6g, 5g deionizations are added dropwise under the conditions of being stirred at room temperature
2h is stirred at room temperature in water.By after hydrolysis N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane, N- (2- amino-ethyls)-
TSL 8330 is added dropwise under stirring at room temperature in 20wt% montmorillonite aqueous solutions, is stirred 1h, is then started to steam
It evaporates, temperature is slowly raised to be added dropwise 50ml toluene while stirring in the process, does not have fraction in temperature-rise period until temperature reaches 115
DEG C, distillation obtains the sample after removal solvent (toluene, methanol, water), then passes through revolving again until without fraction (about 4-5h)
Remaining solvent is all removed, obtains silane-modified nano imvite paste.The silane-modified nanometers of 0.1g are weighed to cover
De- soil paste is dissolved in N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane of 200ml and N- (2- amino-ethyls)-ammonia
In the mixed solution of base propyl trimethoxy silicane (in the mixed solution, N- (2- amino-ethyls)-isobutyl methyl dimethoxy
The volume ratio of base silane and N- (2- amino-ethyls)-TSL 8330 is 1:1) it is, first equal under conditions of stirring
It is even to be dispersed into graininess, obtain the dispersion liquid containing nano imvite silane-modified 0.05wt% using ultrasonic 40min.It should
Dispersion liquid is transparent uniform liquid.
Embodiment 5
The aqueous montmorillonites of 1.0g (clay) are added in 100ml deionized waters while stirring, 1wt% montmorillonite water is made
Solution.N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (molal weight 206g/mol) 20g are measured, room temperature is stirred
8g deionized waters are added dropwise under the conditions of mixing, 2h is stirred at room temperature.By the N- β after hydrolysis-(aminoethyl)-γ-aminopropyltriethoxy dimethoxy
Base silane is added dropwise under stirring at room temperature in 1wt% montmorillonite aqueous solutions, is stirred 1h, is then started to distill, temperature slowly increases
During 440ml toluene is added dropwise while stirring, there is no fraction in temperature-rise period until temperature reaches 115 DEG C, distillation is not until have
There is fraction (about 4-5h), obtain the sample after removal solvent (toluene, water), then again all removed remaining solvent by rotating
It goes, obtains silane-modified nano imvite paste.It weighs the silane-modified nano imvite pastes of 0.1g and is dissolved in 0.5ml
N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane in, first graininess is uniformly dispersed under conditions of stirring,
The dispersion liquid containing nano imvite silane-modified 20wt% is obtained using ultrasonic 40min.
Fig. 1 gives the photo of the dispersion liquid of silane-modified nano imvite that embodiment 5 is prepared, can from figure
To find out it as transparent uniform liquid.
Embodiment 6
The aqueous montmorillonites of 1.0g (clay) are added in 100ml deionized waters while stirring, 1wt% montmorillonite water is made
Solution.Measure N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane (molal weight 220g/mol) 20g, 3- ammonia third
30ml methanol is added dropwise to form silicon in base dimethylethoxysilane (molal weight 161g/mol) 10g under the conditions of being stirred at room temperature
Alkane solution is added dropwise 10g deionized waters after mixing, 2h is stirred at room temperature again.By N- (2- amino-ethyls)-isobutyl methyl after hydrolysis
Dimethoxysilane, 3- aminopropyl dimethylethoxysilanes, are added dropwise under stirring at room temperature in 1wt% montmorillonite aqueous solutions,
1h is stirred, then starts to distill, temperature is slowly raised to be added dropwise 220ml toluene while stirring in the process, does not have in temperature-rise period
Fraction is until temperature reaches 115 DEG C, and distillation is until without fraction (about 4-5h), after obtaining removal solvent (toluene, methanol, water)
Then remaining solvent by revolving is all removed, obtains silane-modified nano imvite paste by sample again.It weighs
Nano imvite paste silane-modified 0.1g is dissolved in N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane of 1ml
With in the mixed solution of 3- aminopropyl dimethylethoxysilanes (in the mixed solution, N- (2- amino-ethyls)-isobutyl group first
The volume ratio of base dimethoxysilane and 3- aminopropyl dimethylethoxysilanes is 1:1), first uniformly divide under conditions of stirring
Graininess is dissipated into, the dispersion liquid containing nano imvite silane-modified 10wt% is obtained using ultrasonic 40min.The dispersion liquid
For transparent uniform liquid.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of transparent silane-modified nano imvite dispersion liquid, which is characterized in that its composition contains：
a：Silane-modified nano imvite, weight percent are 0.01~30wt%, preferably 0.1~20wt%；
b：Decentralized medium, weight percent are 70~99.99wt%, preferably 80~99.9wt%；
Wherein, the decentralized medium includes b-1) silicone fluid medium；
The b-1) silicone fluid medium is silane and its partial hydrolysis condensation product, account for the weight percent of decentralized medium
For 30~100wt%；
Wherein, the sum of weight percent of each component is 100wt% in dispersion liquid.
2. silane-modified nano imvite dispersion liquid according to claim 1, which is characterized in that in the decentralized medium
Further include b-2) organic solvent medium and b-3) azeotropic solvent medium；The b-2) organic solvent medium accounts for the weight of decentralized medium
Amount percentage is 0~65wt%；The b-3) azeotropic solvent medium account for decentralized medium weight percent be 0~5wt%.
3. silane-modified nano imvite dispersion liquid according to claim 1 or 2, which is characterized in that the nanometer is covered
The grain size of soil is taken off between 200~400 mesh.
Preferably, the nano imvite is water nano montmorillonite.
Preferably, the water nano montmorillonite is selected from sodium base nano imvite, calcium base nano imvite, Sodium/Calcium base nanometer
Montmorillonite or magnesium-base nano montmorillonite.
Preferably, the water nano montmorillonite is selected from sodium base nano imvite or Sodium/Calcium base nano imvite.
4. the silane-modified nano imvite dispersion liquid according to any one of claim 1-3 claims, feature
It is, the silane is selected from DfOne or more of mixture or selected from DfOne or more of and Tf、Mf, in M
One or more of mixtures, the Df、Tf、Mf, M have following molecular formula：
Wherein,
Df、MfIt is identical or different with the R in M, it is independently from each other C1-6Alkyl, C2-6Alkenyl, C6-14Aryl, C3-10Alkyl oxy
(methyl) acrylate-based and C3-10Alkyl oxy epoxy C3-10Alkyl, when containing more than two R, each R is identical or different；
Df、Tf、MfIt is identical or different with the R' in M, it is independently from each other H, C1-6Alkyl, when containing more than two R', respectively
A R' is identical or different；
Df、TfAnd MfIn RfIt is identical or different, it is independently from each other-(CxH2x)-[NH-(CH2)m]n-NH2Or-(CyH2y)-
NH-(CzH2z)-[CHO(CH3)CH2]k-NH2, wherein, x is the integer between 1 to 11, and n is the integer between 0 to 5, and m is 1 to 6
Between integer, y, z be 1 to 6 between integer, k be 1 to 5 between integer.
Preferably, R is selected from methyl, ethyl, isopropyl, propyl, butyl, isobutyl group, vinyl, acrylic, phenyl, propoxyl group third
Olefin(e) acid ester group, propoxy methyl be acrylate-based and propoxyl group glycidyl, and when containing more than two R, each R is identical or not
Together.
Preferably, R' is selected from H, methyl, ethyl, isopropyl, propyl, butyl and isobutyl group, each when containing more than two R'
R' is identical or different.
Preferably, RfSelected from-(CyH2y)-NH-(CzH2z)-[CHO(CH3)CH2]k-NH2Or-(CH2)x[NH(CH2)m]nNH2,
In, y, z be 2 to 4 between integer, k be 1 to 3 between integer, x 1,3,4,11, n be 0 to 3 between integer, m 2,
6。
Preferably, RfSelected from-CH2CH2CH2NHCH(CH3)CH2[CHO(CH3)CH2]2NH2Or-CH2CH(CH3)CH2NHCH2CH2NH2
One or both of.
Preferably, the silane be selected from N- (2- amino-ethyls)-isobutyl methyl dimethoxysilane or N- β-(aminoethyl)-
The mixture of one or both of γ-aminopropyltriethoxy dimethoxysilane or selected from N- (2- amino-ethyls)-isobutyl group first
One or both of base dimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and 3- aminopropyls
The mixture of one or both of dimethylethoxysilane, N- (2- amino-ethyls)-TSL 8330.
Preferably, D in the silanefWeight percent >=30wt% (preferably, weight percent >=50wt%), the weight of M
Percentage≤10wt% (preferably, weight percent≤5wt%).
5. the silane-modified nano imvite dispersion liquid according to any one of claim 1-4 claims, feature
Be, the b-1) silicone fluid medium be above-mentioned formula Df、Tf、Mf, silane and its partial hydrolysis condensation product shown in M.
Preferably, the b-2) organic solvent medium be selected from methanol, ethyl alcohol, isopropanol, normal propyl alcohol, just (different) butanol, acetone,
Tetrahydrofuran, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol, glycol monoethyl ether, glycol dimethyl ether,
One or more of acetonitrile, ethyl acetate, aniline, methyl ethyl ketone, pyridine, acetic acid.
Preferably, the b-3) azeotropic solvent medium be selected from ethyl alcohol, just (different) propyl alcohol, just (different) butanol, ether, chloroform, two
Chloroethanes, benzene,toluene,xylene, methyl phenyl ethers anisole, phenetole, dioxane, ethyl acetate, tetrahydrofuran, pyridine, formic acid, acetic acid
In one kind.
6. the preparation method of the silane-modified nano imvite dispersion liquid described in any one of claim 1-5 claims,
The preparation method includes the following steps：
1) prepared by hydrolyzed silane solution：Solution of silane with water is mixed, prepares the hydrolyzed silane solution；
2) under stiring, nano imvite is dispersed in water to form transparent dispersion；
3) hydrolyzed silane solution that step 1) is prepared is added in the dispersion that step 2) is prepared, and be added portionwise
Azeotropic solvent distills out the azeotropic liquid of organic solvent, water and azeotropic solvent；When no azeotropic liquid distillates, optionally, remove remaining
Part or all of solvent, obtain paste；
4) silane solution is added dropwise in the paste that step 3) is prepared, that is, be prepared transparent silane-modified
Nano imvite dispersion liquid.
7. the preparation method of silane-modified nano imvite dispersion liquid according to claim 6, which is characterized in that in step
It is rapid that the solution of silane is the mixed liquor of silane and organic solvent 1) and in step 4), wherein, the matter of silane in solution of silane
Measure a concentration of 1~100wt%.
Preferably, the organic solvent in the solution of silane is selected from methanol, ethyl alcohol, isopropanol, just normal propyl alcohol, (different) butanol, third
Ketone, tetrahydrofuran, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol, glycol monoethyl ether, glycol dinitrate
One or more of ether, acetonitrile, ethyl acetate, aniline, methyl ethyl ketone, pyridine, acetic acid.
Preferably, in step 1), the preparation condition of the hydrolyzed silane solution is：After the solution of silane is mixed with water, 0
0.5~10h is stirred at~80 DEG C, it is preferable that 0.5~6h is stirred at 10~50 DEG C.
Preferably, in step 1), the molar ratio of the silane and water is 1:0.1~25, preferably 1:0.5~20；Into one
Step preferably 1:0.5~6.
Preferably, in step 2), the nano imvite is preferably grain size between 200~400 mesh.
Preferably, the cation exchange capacity of the nano imvite is 50~300mmol/100g, it is preferable that the nanometer is covered
The cation exchange capacity for taking off soil is 80~150mmol/100g.
Preferably, in step 2), it is the saturating of 0.01~50wt% that the nano imvite, which is dispersed in water and to form mass concentration,
Bright dispersion.
Preferably, the nano imvite is dispersed in water the transparent dispersion system to form that mass concentration is 0.1~30wt%.
8. the preparation method of the silane-modified nano imvite dispersion liquid described according to claim 6 or 7, which is characterized in that
In step 3), the hydrolyzed silane solution is added dropwise in the dispersion, the mass ratio of montmorillonite and silane
It is 1:0.1~30 (preferably 1:1~20) stirring 0.5~(preferably, stirred at 10~50 DEG C for 24 hours, and at 0~80 DEG C
0.5~12h), and azeotropic solvent is added portionwise, the azeotropic liquid of gradually heat up, distill out organic solvent, water and azeotropic solvent, directly
To when being supplemented azeotropic solvent distillation, no azeotropic liquid distillates.
Preferably, in step 3), when no azeotropic liquid distillates, optionally, remaining portion is removed by distillation or rotary evaporation
Point or whole solvent, you can paste is prepared.
Preferably, in step 3), the azeotropic solvent be selected from ethyl alcohol, just (different) propyl alcohol, just (different) butanol, ether, chloroform,
Dichloroethanes, benzene,toluene,xylene, methyl phenyl ethers anisole, phenetole, dioxane, ethyl acetate, tetrahydrofuran, pyridine, formic acid, second
One kind in acid.
9. the preparation side of the silane-modified nano imvite dispersion liquid according to any one of claim 6-8 claims
Method, which is characterized in that in step 4), stirring and ultrasound condition carry out it is lower by solution of silane be added dropwise to step 3) prepare
In obtained paste, that is, transparent silane-modified nano imvite dispersion liquid is prepared.
Preferably, in step 4), modified nano imvite in the transparent silane-modified montmorillonite dispersions
Mass concentration is 0.01~30wt%, preferably 1~20wt%
Preferably, in step 4), silane and its partial hydrolysis contracting in the transparent silane-modified montmorillonite dispersions
The mass concentration for closing product and organic solvent medium is 70~99.99wt%, preferably 80~99wt%.
10. prepared in the silane-modified nano imvite dispersion liquid or claim 6-9 described in claim 1-5 obtain
Silane-modified nano imvite dispersion liquid application, which is characterized in that can be as the additive of packaging material, as saturating
The auxiliary agent of bright material, can also increase the intensity of product, barrier properties for gases, adjustment Refractive Index of Material, reinforcing material anti-flammability,
The heat-resisting performances such as water-fast of the flatness of material surface, material.
Preferably, the silane-modified nano imvite dispersion liquid can be applied in optical material, such as by the material
Applied in LED encapsulation material.
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| CN113372813A (en) * | 2021-05-17 | 2021-09-10 | 上海电力大学 | Preparation method of montmorillonite/sol-gel composite coating |
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