CN105597561A - Preparation method and application of organosilicone sol based on pH swing - Google Patents

Preparation method and application of organosilicone sol based on pH swing Download PDF

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Publication number
CN105597561A
CN105597561A CN201510998584.0A CN201510998584A CN105597561A CN 105597561 A CN105597561 A CN 105597561A CN 201510998584 A CN201510998584 A CN 201510998584A CN 105597561 A CN105597561 A CN 105597561A
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organic silicon
silicon sol
preparation
organosilicone
water
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CN105597561B (en
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徐荣
郭猛
钟璟
张琪
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Changzhou University
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Changzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/025—Aluminium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/48—Influencing the pH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/32—Melting point or glass-transition temperatures

Abstract

The invention belongs to the field of preparation of inorganic membrane materials, in particular to a preparation method and application of an organosilicone sol based on pH swing. The preparation method comprises the following steps of adding an organosilicone source precursor into absolute ethyl alcohol; after stirring in water bath, adding deionized water; on the premise of continuous stirring in the water bath, adjusting the pH of the system to acidity by using acid and reacting for one hour; adjusting the pH of the system to weak acidity or neutrality, and reacting for one hour to prepare the organosilicone sol of which particle size distribution is extremely-narrow and stable; gelatinizing the sol into a membrane for reverse osmosis desalination. The organosilicone reverse osmosis membrane shows excellent hydrothermal stability and salt rejection rate.

Description

A kind of organic silicon sol preparation method and application swinging based on pH
Technical field
The invention belongs to inorganic material film preparation field, particularly a kind of based on pH swing organic silicon sol preparation method andApplication.
Background technology
Along with being on the rise of water resources problems, by reverse osmosis technology by seawater and brackish water desalination or process industrial wastewater and becomeObtain the effective way of fresh water. The selection of reverse osmosis membrane material is a step the most key in reverse osmosis technology. With polysulphone super-filter membraneFor the commodity PA membrane of supporter is the reverse osmosis membrane of present main flow, still, such membrane material overwhelming majority can only 50 DEG C withLower use, has limited the application of reverse osmosis membrane material in industrial production greatly.
For example, in textile industry, the leaving water temperature of bleaching and dyeing waste water can be up to 90 DEG C, if use high temperature resistant counter-infiltrationFilm, can directly carry out membrane separation and will waste water cooling, thereby can save equipment investment, reduce energy consumption, improve waterFlux. Therefore, the novel high temperature resistant reverse osmosis composite membrane tool of exploitation one class is of great significance.
Summary of the invention
Have the poor shortcoming of heat-resisting quantity for traditional polyamide reverse osmose membrane, the present invention proposes to ensure film in reverse osmosis processSalt rejection and the prerequisite of water flux under, prepare a kind of method that can resistant to elevated temperatures reverse osmosis membrane.
For achieving the above object, the present invention selects and contains the organosilicon source presoma that C-C bridge linkage group or side contain C chain,In colloidal sol preparation process by adopting pH swinging method to prepare that particle diameter is especially little, particle diameter distributes narrow especially and very stable havingMachine Ludox, is coated in this colloidal sol with α-Al2O3For on the support diaphragm of material through high-temperature calcination film forming,
Concrete steps are as follows:
Organosilicon source presoma is joined in absolute ethyl alcohol, after stirring in water bath, add deionized water, and in water-bath continuous stirringUnder prerequisite, with sour, the pH of system is adjusted to acidity, reaction 1h; Again the pH of system is adjusted to faintly acid or neutrality, andReaction 1h, prepares organic silicon sol,
Wherein, organosilicon source presoma is 1,2-bis-(triethoxy is silica-based) ethane (BTESE), 1,2-bis-(triethoxy is silica-based)One or more in ethene (BTESEthy), ethyl trimethoxy silane (ETMS), ethyl triethoxysilane (ETTS),
Bath temperature is 25～40 DEG C, speed of agitator 500rpm,
The acid adopting is concentrated hydrochloric acid, and the pH value of regulation system is 0.7～1.0; By ammoniacal liquor, the pH of system is adjusted to 6～7 again.
The present invention also provides a kind of technique of utilizing above-mentioned organic silicon sol to prepare reverse osmosis membrane, is specially: by what prepareOrganic silicon sol is coated in α-Al2O3On support diaphragm for material, under hot conditions, calcine film forming, this film is applied to reverse osmosisIn saturating desalination field, and show excellent hydrothermal stability and desalting performance,
Wherein, being sintered into film temperature is 100-300 DEG C.
Beneficial effect of the present invention is: under separate acid catalytic condition, due in hydrolysate-OH group is more and more to be caused beingThe positive charge of transition state is more and more unstable, and hydrolysis reaction is also slack-off gradually; Separately in base catalyzed reactions process due to-OHThe generation of group makes electronegative transition state more and more stable, and hydrolysis reaction becomes again after accelerating gradually to arrive balance graduallySlowly. After reaction finishes, because catalyst is still present in colloidal sol, the network structure of colloidal sol is still increasing very slowly, grainFootpath is also slowly becoming large.
The present invention after acid catalyzed reaction finishes, add in alkali and colloidal sol in whole or most of acid, control is reacted and is rested on certainIndividual moment, instant micelle footpath is controlled at certain particular range. Soda acid replaces catalysis and has avoided reacting under separate acid catalytic conditionAfter finishing, colloidal sol particle diameter still constantly becomes large shortcoming, has effectively controlled colloidal sol particle diameter and has distributed; Overcome independent base catalysis simultaneouslyWater Under solution speed is too fast also accelerates polymerisation simultaneously, and polycondensation product collision frequently causes that colloidal sol is unstable, grainThe shortcoming of the large and wider distribution in footpath. Soda acid replaces catalysis and can overcome the shortcoming of separate acid, base catalysis, controls colloidal sol reaction process,In order to prepare, particle diameter is especially little, particle diameter distributes, and narrow and stable especially organic silicon sol provides a kind of effective ways.
The present invention prepares after film forming the colloidal sol preparing for reverse osmosis deaslination, organic owing to introducing in silicon network structureC-C bridge linkage group or side C chain, greatly suppressed hydrolysis and the rearrangement of Si-O-Si structure. This film is water-soluble at 90 DEG CIn liquid, still show fabulous high-temperature stability. Overcome the PA membrane of tradition taking polysulfones as supporter be difficult to 50 DEG C withOn environment in the problem that uses, expanded the application of reverse osmosis membrane, tool is of great significance.
Brief description of the drawings
Fig. 1 is that embodiment 1, comparative example 1-1, comparative example 1-2 prepare gained colloidal sol particle diameter distribution map;
Fig. 2 is that embodiment 2, comparative example 2-1, comparative example 2-2 prepare gained colloidal sol particle diameter distribution map;
Fig. 3 is that the organosilicon membrane prepared of embodiment 1 is for the reverse osmosis deaslination performance map under the temperature cycles condition up to 90 DEG C;
To be that embodiment 1, comparative example 1-1 are fresh prepare colloidal sol and leave standstill colloidal sol particle diameter distribution map after 10 days Fig. 4.
Detailed description of the invention
Embodiment 1
1. 1gBTESE is dissolved in 15.59g absolute ethyl alcohol (EtOH) solution to 40 DEG C of stirring in water bath 5min, rotating speed 500rpm;In solution, add 3.05g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; BTESE:EtOH:H2O=1:120:60 (mol ratio);
2. be 37% concentrated hydrochloric acid to adding solute mass fraction in above-mentioned mixed solution, regulating mixed solution pH is 0.8,40 DEG CContinuous stirring reaction 1h under water bath condition, rotating speed 500rpm;
3. in mixed solution, slowly add ammoniacal liquor again, regulate mixed solution pH to react 1h under 6.5,40 DEG C of water bath condition,Rotating speed 500rpm, prepares bridging organic silicon sol;
4. the colloidal sol preparing is coated in α-Al2O3(become thickness for calcine film forming on the support diaphragm of material at 200 DEG CDegree is 60nm) and be applied in reverse osmosis deaslination.
Embodiment 2
1. 1gETMS is dissolved in 36.79gEtOH to 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; In solutionAdd 7.2g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; ETMS:EtOH:H2O＝1：120:60 (mol ratio);
2. be 37% concentrated hydrochloric acid to adding solute mass fraction in above-mentioned mixed solution, regulating mixed solution pH is 0.8,40 DEG CContinuous stirring reaction 1h under water bath condition, rotating speed 500rpm;
3. in mixed solution, slowly add ammoniacal liquor again, regulate mixed solution pH to react 1h under 7,40 DEG C of water bath condition, turnSpeed 500rpm, prepares side chain organic silicon sol;
4. the colloidal sol preparing is coated in α-Al2O3(become thickness for calcine film forming on the support diaphragm of material at 200 DEG CDegree is 60nm) and be applied in reverse osmosis deaslination.
Comparative example 1-1
1. 1gBTESE is dissolved in 15.59g absolute ethyl alcohol (EtOH) solution to 40 DEG C of stirring in water bath 5min, rotating speed 500Rpm; In solution, add 3.05g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; BTESE:EtOH：H2O=1:120:60 (mol ratio);
2. be 37% concentrated hydrochloric acid to slowly adding solute mass fraction in above-mentioned mixed solution, regulating mixed solution pH is 0.8,Continuous stirring reaction 2h under 40 DEG C of water bath condition, rotating speed 500rpm, makes bridging organic silicon sol. By the bridging preparingOrganic silicon sol is coated in α-Al2O3For calcine film forming (film forming thickness is 60nm) on the support diaphragm of material at 200 DEG CAnd be applied in reverse osmosis deaslination.
Comparative example 1-2
1. 1gBTESE is dissolved in 15.59g absolute ethyl alcohol (EtOH) solution to 40 DEG C of stirring in water bath 5min, rotating speed 500Rpm; In solution, add 3.05g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; BTESE: EtOH：H2O=1:120:60 (mol ratio);
2. in above-mentioned mixed solution, slowly add ammoniacal liquor, regulate mixed solution pH to stir continuously under 13,40 DEG C of water bath conditionMix reaction 2h, rotating speed 500rpm, prepares bridging organic silicon sol. The bridging organic silicon sol preparing is coated inWith α-Al2O3De-for calcining film forming (film forming thickness is 60nm) on the support diaphragm of material and be applied to counter-infiltration at 200 DEG CIn salt.
Comparative example 2-1
1. 1gETMS is dissolved in 36.79gEtOH to 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; In solutionAdd 7.2g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; ETMS:EtOH:H2O＝1：120:60 (mol ratio);
2. be 37% concentrated hydrochloric acid to adding solute mass fraction in above-mentioned mixed solution, regulating mixed solution pH is 0.8,40 DEG CContinuous stirring reaction 2h under water bath condition, rotating speed 500rpm, prepares side chain organic silicon sol. By the side chain preparingOrganic silicon sol is coated in α-Al2O3For calcine film forming (film forming thickness is 60nm) on the support diaphragm of material at 200 DEG CAnd be applied in reverse osmosis deaslination.
Comparative example 2-2
1. 1gETMS is dissolved in 36.79gEtOH to 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; In solutionAdd 7.2g deionized water (H2O), continue 40 DEG C of stirring in water bath 5min, rotating speed 500rpm; ETMS:EtOH:H2O＝1：120:60 (mol ratio);
2. in above-mentioned mixed solution, slowly add ammoniacal liquor, regulate mixed solution pH to stir continuously under 13,40 DEG C of water bath conditionMix reaction 2h, rotating speed 500rpm, prepares side chain organic silicon sol. The side chain organic silicon sol preparing is coated inWith α-Al2O3De-for calcining film forming (film forming thickness is 60nm) on the support diaphragm of material and be applied to counter-infiltration at 200 DEG CIn salt.
The reverse osmosis membrane of preparing in table 1 embodiment, comparative example is reverse osmosis deaslination performance comparison at 90 DEG C
Can be reached a conclusion by table 1 and accompanying drawing (1,2,3,4): the water flux of the reverse osmosis membrane of being prepared by method of the present invention andSalt rejection is significantly improved with respect to conventional method, and still shows fabulous hydrothermal stability under 90 DEG C of conditions. ThisBright prepared colloidal sol particle diameter is especially little, distribution is narrow especially.

Claims (8)

1. an organic silicon sol preparation method who swings based on pH, is characterized in that: described preparation method is, by organicSilicon source presoma joins in absolute ethyl alcohol, adds deionized water after stirring in water bath, and under the prerequisite of water-bath continuous stirring, usesThe pH of system is adjusted to acidity by acid, reaction 1h; Again the pH of system is adjusted to faintly acid or neutrality, and reacts 1h,Prepare organic silicon sol.
2. the organic silicon sol preparation method who swings based on pH as claimed in claim 1, is characterized in that: described is organicSilicon source presoma is 1,2-bis-(triethoxy is silica-based) ethane, 1,2-bis-(triethoxy is silica-based) ethene, ethyl trimethoxy silane,One or more in ethyl triethoxysilane.
3. the organic silicon sol preparation method who swings based on pH as claimed in claim 1, is characterized in that: described water-bathTemperature is 25～40 DEG C.
4. the organic silicon sol preparation method who swings based on pH as claimed in claim 1, is characterized in that: described stirringRotating speed is 500rpm.
5. the organic silicon sol preparation method who swings based on pH as claimed in claim 1, is characterized in that: adopt concentrated hydrochloric acidThe pH value of regulation system is 0.7～1.0.
6. the organic silicon sol preparation method who swings based on pH as claimed in claim 1, is characterized in that: by ammoniacal liquor againThe pH of system is adjusted to faintly acid or neutrality, and described pH value is 6～7.
7. the application of organic silicon sol as prepared in claim 1 to 6 any one, is characterized in that: described in be applied as, profitPrepare reverse osmosis membrane with described organic silicon sol,
Preparation technology is that preparation-obtained organic silicon sol is coated in α-Al2O3On support diaphragm for material, high temperatureUnder condition, calcine film forming.
8. the application of organic silicon sol as prepared in claim 7, is characterized in that: being sintered into film temperature is 100-300 DEG C.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106110906A (en) * 2016-07-15 2016-11-16 常州大学 A kind of preparation method of hydrophilic organic silicon film
CN107138133A (en) * 2017-05-18 2017-09-08 常州大学 A kind of preparation method for being used to remove the high-efficiency adsorbent of cadmium ion in water
CN110885399A (en) * 2019-11-26 2020-03-17 李航静 Acrylic emulsion adhesive and preparation method thereof
CN111359446A (en) * 2020-03-09 2020-07-03 常州大学 Preparation method and application of acid-resistant PSQ composite film
CN111603950A (en) * 2020-06-03 2020-09-01 常州大学 Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof
CN113648855A (en) * 2021-08-27 2021-11-16 常州大学 For separating CO2/N2Method for preparing organic silicon film

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CN101913175A (en) * 2010-07-15 2010-12-15 中国林业科学研究院木材工业研究所 Method for preparing wood with flame-retardant and light-emitting functions
CN105148753A (en) * 2015-08-31 2015-12-16 中国科学院宁波材料技术与工程研究所 Organic-inorganic hybrid SiO<2> membrane with CO<2> preferable permeation function and method for preparing organic-inorganic hybrid SiO<2> membrane

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Publication number Priority date Publication date Assignee Title
US6494326B1 (en) * 2000-06-15 2002-12-17 Sandia Corporation Composite zeolite membranes
CN1883780A (en) * 2006-05-30 2006-12-27 天津大学 Process for preparing silicon separating films with specialized selectivity to natural products
CN101913175A (en) * 2010-07-15 2010-12-15 中国林业科学研究院木材工业研究所 Method for preparing wood with flame-retardant and light-emitting functions
CN105148753A (en) * 2015-08-31 2015-12-16 中国科学院宁波材料技术与工程研究所 Organic-inorganic hybrid SiO<2> membrane with CO<2> preferable permeation function and method for preparing organic-inorganic hybrid SiO<2> membrane

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106110906A (en) * 2016-07-15 2016-11-16 常州大学 A kind of preparation method of hydrophilic organic silicon film
CN106110906B (en) * 2016-07-15 2018-10-19 常州大学 A kind of preparation method of hydrophilic organic silicon film
CN107138133A (en) * 2017-05-18 2017-09-08 常州大学 A kind of preparation method for being used to remove the high-efficiency adsorbent of cadmium ion in water
CN110885399A (en) * 2019-11-26 2020-03-17 李航静 Acrylic emulsion adhesive and preparation method thereof
CN110885399B (en) * 2019-11-26 2021-12-07 新丰杰力电工材料有限公司 Acrylic emulsion adhesive and preparation method thereof
CN111359446A (en) * 2020-03-09 2020-07-03 常州大学 Preparation method and application of acid-resistant PSQ composite film
CN111359446B (en) * 2020-03-09 2022-03-01 常州大学 Preparation method and application of acid-resistant PSQ composite film
CN111603950A (en) * 2020-06-03 2020-09-01 常州大学 Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof
CN111603950B (en) * 2020-06-03 2022-04-22 常州大学 Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof
CN113648855A (en) * 2021-08-27 2021-11-16 常州大学 For separating CO2/N2Method for preparing organic silicon film
CN113648855B (en) * 2021-08-27 2022-08-02 常州大学 For separating CO 2 /N 2 Method for preparing organic silicon film

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