CN104084064B - The preparation method of a kind of silane or halogenated silanes modified cellulose gas separation membrane - Google Patents
The preparation method of a kind of silane or halogenated silanes modified cellulose gas separation membrane Download PDFInfo
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- CN104084064B CN104084064B CN201410226856.0A CN201410226856A CN104084064B CN 104084064 B CN104084064 B CN 104084064B CN 201410226856 A CN201410226856 A CN 201410226856A CN 104084064 B CN104084064 B CN 104084064B
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Abstract
Cellulose gas separation membrane that the invention discloses a kind of silane or halogenated silanes modification and preparation method thereof, improves the method for the gas separating property of material by chemical modification.Cellulose acetate or NC Nitroncellulose are dissolved in solvent by the present invention; After obtaining the polymer solution of homogeneous phase, in solution, add silane or halogenated silanes; After question response completes, solution is spent aqueous ionomer gel, is rinsed well with the mixed solution of deionized water and methyl alcohol after complete gel, by the silylation cellulose dissolution that obtains in a solvent, by coating device striking film forming on non-woven fabrics, be then separated in immersion precipitation bath film forming.Film prepared by the method has good permeability and selective and good industrial applications.
Description
Technical field
The present invention relates to the preparation method of the cellulose gas separation membrane of a kind of silane and halogenated silanes modification, be applied particularly to the field as gas and steam diffusion barrier.
Background technology
Cellulose is a kind of natural macromolecular material of rich reserves, its filming performance is excellent, desalination and gas separating property higher, with low cost, Chemical Physics stable performance and environmentally friendly, makes cellulose and its derivates can apply the field be separated with functional membranes such as such as desalinization, gas separaion and infiltration evaporations widely.
Cellulose makes it be difficult to directly utilize owing to having good solvent resistance.People can select suitable dissolution with solvents cellulose, spin out hollow-fibre membrane by phase separation method, and Chinese patent CN1,485,125A describe in detail this process.The obtained hollow-fibre membrane of this process is homogeneous compact texture, and compared with industrialized asymmetric membrane, although improve selective to gas of membrane material, the permeance property of this film to gas is lower, and the use industrially made is restricted.
US Patent No. 4,735,193 and US5,127, adopt in 925 adsorptivity particles filled enter CAM matrix in, make the mixed substrate membrane containing nano-grade molecular sieve of organic inorganic hybridization.By this operation, change the gas permeability of membrane material intrinsic, provide the free degree of a regulation and control membrane material permselective property.While lifting Gas Separation Membrane Performance, add inorganic fill particle, enhance the mechanical performance of membrane material.But due to the impact added polymer phase separation of the restriction in inorganic particle size and particle, limit the commercial Application of successfully obtained mixed substrate membrane containing nano-grade molecular sieve to a certain extent.
Summary of the invention
In order to improve selectivity, the permeance property of film and better be applied to suitability for industrialized production, the present invention proposes a kind of by chemical modification process cellulose family membrane material, by silylation modification, the cellulosic gas separating property of silylation of gained obtains change in various degree on original basis.
For realizing object of the present invention, concrete grammar comprises following aspect:
A preparation method for the cellulose gas separation membrane of silane or halogenated silanes modification, the method comprises the steps:
(1) cellulose acetate or NC Nitroncellulose are dissolved in solvent, described solvent comprises molten water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, benzene,toluene,xylene, acetone, ether, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, n-hexane, normal heptane, isooctane, 1,2-difluoro tetrachloroethanes, 1,1,2-trifluorotrichloroethane, 1,1, one or more in 2,2-tetrafluorodichloroethane, benzinum or IsoParG;
(2) in the homogeneous polymer solution obtained, silane or halogenated silanes is added, after at the temperature of 0-150 DEG C, reaction terminates, solution is spent aqueous ionomer gel, is rinsed to its conductance lower than 20 μ s/cm with the mixed solution of deionized water and methyl alcohol after complete gel; Silane or halogenated silanes mass concentration is in the solution 10-20%;
(3) by the silylation cellulose dissolution that obtains in a solvent, described solvent is water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, benzene,toluene,xylene, acetone, ether, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, n-hexane, normal heptane, isooctane, 1,2-difluoro tetrachloroethanes, 1,1,2-trifluorotrichloroethane, 1, one or more in 1,2,2-tetrafluorodichloroethane, benzinum or IsoParG; By coating device striking film forming on non-woven fabrics, be then separated in immersion precipitation water-bath film forming.
Asymmetric membrane is by doing/wetting phase partition method preparation.Cellulosic polymer is dissolved in coordinative solvent in (1) by step, to be dissolved completely after, add silane or halogenated silanes, at 0-150 DEG C, preferred 20-50 DEG C, passes into protection gas, preferred nitrogen; After reaction terminates, volume ratio solution being injected deionized water and methyl alcohol is the mixed solution gel of 1:1, cleans, until the conductance of cleaning fluid is lower than 20 μ s/cm after gel with the mixed solution of methyl alcohol and pure water again.Then use knifing machine blade coating on non-woven fabrics, make phase-splitting in the water-bath of primary membrane immersion precipitation obtain asymmetric rolled film by driven by motor non-woven fabrics.The spinning of hollow-fibre membrane adopts nitrogen that solution is extruded spinning storage tank, measuring pump is entered after filtration after net filtration, be pumped into spinning head by measuring pump again, the birth film extruded in spinning head is entering in gel water-bath after the dry journey of certain altitude, and bath temperature is room temperature.Core liquid is controlled to be pressed in the inner chamber of spinning head from storage tank by constant-flux pump.The fiber obtained can be collected and immerse in exchange of solvent liquid after suitable stretching, rinsing, carries out drying and process and load the cellulose gas separation membrane as obtained modification in hollow fibre membrane component after exchange of solvent completes.
The cellulosic modification of silylation is obtained by reacting with cellulose acetate or NC Nitroncellulose in corresponding solvent by silane or halogenated silanes.This kind of method is carried out bulk modified to material, the cellulose derivative of obtained different silylations; Silane group is introduced to change the separating property of membrane component to admixture of gas on film surface.
Above-mentioned cellulose acetate or NC Nitroncellulose be formula (I)
Wherein, substituent group R
1, R
2, R
3in have one at least for hydrogen atom, all the other substituting groups are acetyl group or nitro.
Silane is selected from formula (II), and halogenated silanes is selected from formula (III)
R
1 aSi(XR
2 b)
(4-a)R
a1SiCl
bH
(4-a1-b1)
(II)(III)
Wherein R
1, R
2for univalent alkyl; X be in hydrogen atom, nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms any one; The span of a is the residual valence of the value coupling element X of 0 to 3, subscript b; R can be carbon number from 1 to 20 alkyl, thiazolinyl, aromatic radical, one aralkyl or alkaryl; The span of a1 be 0 to 3, b1 span be 1 to 4 and the residual valence of coupling elements Si.
3-aminopropyl trimethoxysilane is comprised for material modified reactive silane, 3-aminopropyl dimethylethoxysilane, 3-aminopropyl diethoxymethylsilane, 3-aminopropyl triethoxysilane, vinyltrimethoxy silane, VTES, triethoxy (3-isocyano group propyl group) silane, triethoxy (isobutyl group) silane, triethoxyphenylsilan, 3-[two (2-ethoxy) is amino] propane-triethoxysilane, 3-glycydoxy trimethoxy silane, 2-[(acetoxy-methyl) pi-allyl] trimethyl silane, diethoxymethyl [(3-oxiranylmethoxy) propyl group] silane, 3-(trimethoxy first is silica-based) propyl methacrylate.
The halogenated silanes used comprises trim,ethylchlorosilane, chlorotriethyl silane, tributyl chlorosilane, (3-chloropropyl) trimethyl silane, 2-(chloromethyl) pi-allyl-trimethyl silane, vinyl (chloromethyl) dimethylsilane, 3,5-dimethylphenyl chlorosilane, dimethyldichlorosilane, diethyl dichlorosilane, diphenyl dichlorosilane, methyl trichlorosilane, ethyl trichlorosilane, propyltrichlorosilan or tetrachloro silicane.Preferred 3,5-dimethylphenyl chlorosilane.
Alkylated cellulose is the product of cellulose derivative and response type silane, and the gas separation membrane obtained by silylation cellulose is asymmetric plate or asymmetric hollow fiber type.
Beneficial effect:
In the present invention, chemical modification is carried out to membrane material entirety, in the construction unit of cellulose derivative, introduce different silane groups.The introducing of silane group, changes the gas separating property of membrane material, introduces different functional group by means of only simple chemical reaction, and namely controllable membrane material is to the permeability of gas with various mixture and selective.Diffusion barrier prepared by the method, simple to operate, good penetrability, industrialization restriction is little.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, and protection scope of the present invention is not limited to this.Embodiment 1
The cellulose acetate (degree of acetylation DS=2.45) of 11.2g is dissolved in 80gN, in dinethylformamide, to be dissolved completely after add 15g3-aminopropyl dimethylethoxysilane, under 100 DEG C of nitrogen protections, react 24h.After reaction terminates, solution is injected the mixed solution 500mL gel of deionized water and methyl alcohol (volume ratio 1:1), clean 2 times with the mixed solution of methyl alcohol and pure water again after gel, until the conductance of cleaning fluid is lower than 20 μ s/cm.
The silylation cellulose acetate obtained is dissolved in 1-METHYLPYRROLIDONE, add the solution that a certain amount of ethanol is made into polymer residual 15% again, 24h deaeration is placed after obtaining the solution of homogeneous phase, then be expressed in coating device with measuring pump, under driven by motor by uniform for polymer solution blade coating on non-woven fabrics, process through the face of one section of dry journey air knife to primary membrane, Forced convection vaporization falls a certain amount of solvent and non-solvent, convection current terminates in rear immersion precipitation water-bath, and bath temperature is room temperature.After complete gel, film is put into exchange solvent and carry out exchange of solvent, then be positioned over the cellulose acetate asymmetric membrane that air drying obtains the modification of 3-aminopropyl dimethylethoxysilane.After dry, membrane component is at 25 DEG C, and under 10bar pressure, pure carbon dioxide, oxygen, nitrogen and methane are carried out to the testing permeability of gas, the results listed in the following table.
Table 1
Embodiment 2
The cellulose acetate (DS=2.45) of 11.2g is dissolved in 80gN, in dinethylformamide, to be dissolved completely after add 15g VTES, under 100 DEG C of nitrogen protections, react 24h.After reaction terminates, solution is injected the mixed solution 500mL gel of deionized water and methyl alcohol (volume 1:1), clean 2 times with the mixed solution of methyl alcohol and pure water again after gel, until the conductance of cleaning fluid is lower than 20 μ s/cm.
The silylation cellulose acetate obtained is dissolved in 1-METHYLPYRROLIDONE, add the solution that a certain amount of ethanol is made into polymer concentration 30% again, 24h deaeration is placed after obtaining the solution of homogeneous phase, then be expressed in coating device with measuring pump, under driven by motor by uniform for polymer solution blade coating on non-woven fabrics, process through the face of one section of dry journey air knife to primary membrane, Forced convection vaporization falls a certain amount of solvent and non-solvent, convection current terminates in rear immersion precipitation water-bath, and bath temperature is room temperature.After complete gel, film is put into exchange solvent and carry out exchange of solvent, after be positioned over air drying, finally be positioned in vacuum drying oven and under the glass transition temperature of material, it heat-treated, after heat treatment terminates, obtain the cellulose acetate asymmetric membrane of VTES modification.After dry, membrane component is at 25 DEG C, and under 10bar pressure, pure carbon dioxide, oxygen, nitrogen and methane are carried out to the testing permeability of gas, the results listed in the following table.
Table 2
Embodiment 3
The cellulose acetate (DS=1.75) of 22.4g is dissolved in 80gN, in dinethylformamide, to be dissolved completely after add 15g trim,ethylchlorosilane, under 50 DEG C of nitrogen protections, react 24h.After reaction terminates, solution is injected the mixed solution 500mL gel of deionized water and methyl alcohol (1:1), clean 2 times with the mixed solution of methyl alcohol and pure water again after gel, until the conductance of cleaning fluid is lower than 20 μ s/cm.
The silylation cellulose acetate obtained is dissolved in the mixed solution (3:1) of 1-METHYLPYRROLIDONE and acetone, add the solution that a certain amount of ethanol is made into polymer concentration 25% again, 24h deaeration is placed after obtaining the solution of homogeneous phase, then be expressed in coating device with measuring pump, under driven by motor by uniform for polymer solution blade coating on non-woven fabrics, process through the face of one section of dry journey air knife to primary membrane, Forced convection vaporization falls a certain amount of solvent and non-solvent, convection current terminates in rear immersion precipitation water-bath, and bath temperature is room temperature.After complete gel, film is put into and exchanges solvent and carry out exchange of solvent, then be positioned over air drying and obtain trimethyl silane cellulose acetate asymmetric membrane.After dry, membrane component is at 25 DEG C, and under 10bar pressure, pure carbon dioxide, oxygen, nitrogen and methane are carried out to the testing permeability of gas, the results listed in the following table.
Table 3
Embodiment 4
The cellulose acetate (DS=1.75) of 22.4g is dissolved in 80gN, in dinethylformamide, to be dissolved completely after add 15g 3,5-dimethylphenyl chlorosilane and 5g imidazoles, under 50 DEG C of nitrogen protections, react 24h.After reaction terminates, solution is injected the mixed solution 500mL gel of deionized water and methyl alcohol (1:1), clean 2 times with the mixed solution of methyl alcohol and pure water again after gel, until the conductance of cleaning fluid is lower than 20 μ s/cm.
The silylation cellulose acetate obtained is dissolved in the mixed solution (volume ratio 3:1) of 1-METHYLPYRROLIDONE and acetone, add the solution that a certain amount of ethanol is made into polymer concentration 25% again, 24h deaeration is placed after obtaining the solution of homogeneous phase, then be expressed in coating device with measuring pump, under driven by motor by uniform for polymer solution blade coating on non-woven fabrics, process through the face of one section of dry journey air knife to primary membrane, Forced convection vaporization falls a certain amount of solvent and non-solvent, convection current terminates in rear immersion precipitation water-bath, and bath temperature is room temperature.After complete gel, film is put into and exchanges solvent and carry out exchange of solvent, then be positioned over air drying and obtain dimethylphenylsilaneand cellulose acetate asymmetric membrane.After dry, membrane component is at 25 DEG C, and under 10bar pressure, pure carbon dioxide, oxygen, nitrogen and methane are carried out to the testing permeability of gas, the results listed in the following table.
Table 4
Embodiment 5
The cellulose acetate (DS=1.75) of 22.4g is dissolved in 80gN, in dinethylformamide, to be dissolved completely after add 15g bromotrimethylsilane and 5g imidazoles, under 50 DEG C of nitrogen protections, react 24h.After reaction terminates, solution is injected the mixed solution 500mL gel of deionized water and methyl alcohol (1:1), clean 2 times with the mixed solution of methyl alcohol and pure water again after gel, until the conductance of cleaning fluid is lower than 20 μ s/cm.
The silylation cellulose acetate obtained is dissolved in the mixed solution (3:1) of 1-METHYLPYRROLIDONE and acetone, add the solution that a certain amount of ethanol is made into polymer concentration 40% again, 24h deaeration is placed after obtaining the solution of homogeneous phase, then be expressed in coating device with measuring pump, under driven by motor by uniform for polymer solution blade coating on non-woven fabrics, process through the face of one section of dry journey air knife to primary membrane, Forced convection vaporization falls a certain amount of solvent and non-solvent, convection current terminates in rear immersion precipitation water-bath, and bath temperature is room temperature.After complete gel, film is put into and exchanges solvent and carry out exchange of solvent, then be positioned over air drying and obtain dimethylphenylsilaneand cellulose acetate asymmetric membrane.After dry, membrane component is at 25 DEG C, and under 10bar pressure, pure carbon dioxide, oxygen, nitrogen and methane are carried out to the testing permeability of gas, the results listed in the following table.
Table 5
Claims (8)
1. a preparation method for silane or halogenated silanes modified cellulose gas separation membrane, the method comprises the steps:
(1) cellulose acetate or NC Nitroncellulose are dissolved in solvent, described solvent is water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, benzene,toluene,xylene, acetone, ether, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, n-hexane, normal heptane, isooctane, 1,2-difluoro tetrachloroethanes, 1,1,2-trifluorotrichloroethane, 1, one or more in 1,2,2-tetrafluorodichloroethane, benzinum or IsoParG; Forming mass concentration is the solution of 10-30%;
The structure of described cellulose acetate or NC Nitroncellulose be formula (
)
（
）
Wherein, substituent group R
1, R
2, R
3in have one at least for hydrogen atom, all the other substituting groups are acetyl group or nitro;
(2) in the homogeneous polymer solution obtained, silane or halogenated silanes is added, pass into protection gas, after reaction terminates at the temperature of 0-150 DEG C, solution is spent aqueous ionomer gel, rinsed to its conductance lower than 20 μ s/cm with the mixed solution of deionized water and methyl alcohol after complete gel; Silane or halogenated silanes mass concentration is in the solution 10-20%;
(3) by the silylation cellulose dissolution that obtains in a solvent, by coating device striking film forming on non-woven fabrics, be then separated in immersion precipitation water-bath film forming; Alkylated cellulose mass concentration is in the solution 15-40%;
Described solvent is water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, benzene,toluene,xylene, acetone, ether, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE, n-hexane, normal heptane, isooctane, 1,2-difluoro tetrachloroethanes, 1,1,2-trifluorotrichloroethane, 1,1, one or more in 2,2-tetrafluorodichloroethane, benzinum or IsoParG.
2. method according to claim 1, it is characterized in that described silane be formula (
), halogenated silanes be formula (
):
R
1 aSi(XR
2 b)
（4-a）R
a1SiCl
b1H
（4-a1-b1）
（
）（
）
Wherein R
1 ,r
2for univalent alkyl; X be in hydrogen atom, nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms any one; The span of a is the integer in 0-3, and the value of b is the residual valence of coupling element X; R to be carbon number be 1-20 alkyl, thiazolinyl, aromatic radical, one in aralkyl or alkaryl; The span of a1 is the integer in 0-3, and the span of b1 is integer in 1-4 and the residual valence of coupling elements Si.
3. method according to claim 1, is characterized in that the reaction temperature of described step (2) is 20-50 DEG C.
4. method according to claim 1, is characterized in that the halogenated silanes in described step (2) is 3,5-dimethylphenyl chlorosilane.
5. method according to claim 1, is characterized in that the volume ratio of deionized water and methyl alcohol in described step (2) is 1:1.
6. method according to claim 1, while it is characterized in that adding silane or halogenated silanes in described step (2), adds imidazoles, add imidazoles the mass ratio of quality and silane or halogenated silanes be 1:3.
7. method according to claim 1, is characterized in that the protection gas in described step (2) is nitrogen.
8. the method for claim 1, is characterized in that the temperature of gel water-bath in described step (3) is room temperature.
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| US4428776A (en) * | 1982-06-23 | 1984-01-31 | The Standard Oil Company | Cellulosic semipermeable membranes containing silicon compounds |
| CN1142410A (en) * | 1994-05-20 | 1997-02-12 | 液体空气乔治洛德方法利用和研究有限公司 | Improved polymeric Membrane |
| CN1548220A (en) * | 2003-05-09 | 2004-11-24 | 天津膜天膜工程技术有限公司 | Prepn process of cellulose acetate separating membrane |
| CN101816897A (en) * | 2009-02-27 | 2010-09-01 | 同济大学 | ZSM-5 molecular sieve filled silicon rubber/cellulose acetate composite membrane and preparation method thereof |
-
2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4428776A (en) * | 1982-06-23 | 1984-01-31 | The Standard Oil Company | Cellulosic semipermeable membranes containing silicon compounds |
| CN1142410A (en) * | 1994-05-20 | 1997-02-12 | 液体空气乔治洛德方法利用和研究有限公司 | Improved polymeric Membrane |
| CN1548220A (en) * | 2003-05-09 | 2004-11-24 | 天津膜天膜工程技术有限公司 | Prepn process of cellulose acetate separating membrane |
| CN101816897A (en) * | 2009-02-27 | 2010-09-01 | 同济大学 | ZSM-5 molecular sieve filled silicon rubber/cellulose acetate composite membrane and preparation method thereof |
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