CN109012198A - A kind of infiltrating and vaporizing membrane and its preparation and application - Google Patents
A kind of infiltrating and vaporizing membrane and its preparation and application Download PDFInfo
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- CN109012198A CN109012198A CN201810892294.1A CN201810892294A CN109012198A CN 109012198 A CN109012198 A CN 109012198A CN 201810892294 A CN201810892294 A CN 201810892294A CN 109012198 A CN109012198 A CN 109012198A
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- polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- 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
- B01D67/0002—Organic membrane manufacture
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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
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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Abstract
The present invention relates to a kind of infiltrating and vaporizing membranes and preparation method thereof.This method introduces light-initiated curing groups on the existing infiltrating and vaporizing membrane using PDMS as raw material and is made into casting solution with photoinitiator, the casting solution can save for a long time, and substantially reduce the infiltrating and vaporizing membrane cured time after light introducing and reduce the possibility that casting solution penetrates into counterdie, obtained UF membrane efficiency is higher.
Description
Technical field
The invention belongs to technical field of membrane separation, and in particular to a kind of infiltrating and vaporizing membrane and its preparation and application.
Background technique
It is a kind of technique with sustainability that acetone-butanol-ethanol (ABE) fermentation method, which produces butanol, usually with natural production
Object and papermaking wastewater etc. are raw material, and small investment, equipment are compared with simple, mild condition, by-product is few, separation is simple.However,
Since butanol has toxicity, when the concentration of butanol reaches 11g/L in fermentation liquid, about 50% microbes are suppressed
And stop growing, therefore will affect final fermentation concentration, so it is to improve butanol to produce that the butanol of generation is separated in time
The necessary means of rate.
Infiltration evaporation is a kind of new and effective membrane separation technique for separating homogeneous liquid mixture, it utilizes difference
Dissolution of the component in film, diffusion difference, penetrate seperation film with making certain component selections, and penetrating side, the group
Divide and leave infiltrating and vaporizing membrane as a vapor, and the collection that is condensed.Compared with traditional separating technology, infiltration evaporation operation letter
Just, influence that is energy saving and not being segregated solution constant boiling point.Due to the various advantages of infiltration evaporation, it is often used in solution
The removal of a small amount of component.
During infiltration evaporation, it is important to the preparation of infiltrating and vaporizing membrane, traditional using polysiloxanes as raw material
In the preparation process of infiltrating and vaporizing membrane, usually with the PDMS (dimethyl silicone polymer) of terminal hydroxy group sealing end for primary raw material,
TEOS (ethyl orthosilicate) is crosslinking agent, and DBTDL (dibutyl tin dilaurate) is that catalyst synthesizes casting solution, this solidification side
Formula be it is uncontrollable, after catalyst is added, casting solution is unable to maintain that for a long time, just becoming sticky in a few minutes can not scrape
Film, and room temperature or heat cross-linking are generally used after knifing, curing time is longer, it is easy to casting solution be caused to penetrate into bottom
In film, the separating property of film is influenced, this technical bottleneck promote the efficiency of knifing can not, continuous knifing can not be carried out, and
And if being crosslinked at room temperature, need a few hours that can just film be made to be fully cured, limits answering for technology in time
With, prolonged solidification so that casting solution penetrates among counterdie, separating property is affected.
Therefore, how to promote the efficiency of knifing and shorten the film fully crosslinked cured time as urgently to be solved at present
Technical problem.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of infiltration evaporation membrane materials
Material and preparation method thereof.High-efficient and curing time is short using this method film knifing, obtained UF membrane efficiency is higher.
For this purpose, first aspect present invention provides a kind of modified polyorganosiloxane membrane material, molecular structure is as shown in formula I:
In formula I,
R is light-initiated group contained in modifying agent；
R1For polysiloxanes end group；
R2For photoinitiator；
n1、n2And n3For the number of repeat unit of silicon oxygen chain in modified polyorganosiloxane, value is natural number；
M is the number of repeat unit of modified polyorganosiloxane chain in modified polyorganosiloxane membrane material, and value is natural number.
In some embodiments of the invention, the modified polyorganosiloxane membrane material with a thickness of 5-15 μm, contact angle is
103-105°。
Second aspect of the present invention provides a kind of infiltrating and vaporizing membrane comprising modification as described in the first aspect of the invention is poly-
Silicone film material.
In some embodiments of the invention, the infiltrating and vaporizing membrane separates the butanol of 1.5% (v/v) at 45-75 DEG C
The separation factor of aqueous solution is 45-50, flux 700-900L/m2h。
Third aspect present invention provides a kind of preparation method of infiltrating and vaporizing membrane comprising:
Modified polyorganosiloxane and photoinitiator are mixed and made into casting solution by step C；
Step D, by casting solution, knifing, acquisition are coated on the modified polyorganosiloxane liquid film in substrate in substrate；
Step E solidifies the modified polyorganosiloxane liquid film being coated in substrate under illumination condition, is made containing changing
The infiltrating and vaporizing membrane of property polysiloxanes membrane material.
According to the method for the present invention, the modified polyorganosiloxane is made of by the way that light-initiated group is introduced polysiloxanes.
In certain embodiments of the present invention, the modified polyorganosiloxane is reacted with polysiloxanes by modifying agent by light
Cause group introducing polysiloxanes to be made.
In some preferred embodiments of the invention, the modified polyorganosiloxane is gathered by modifying agent with pretreated
Light-initiated group introducing polysiloxanes is made siloxane reactions.
In some further preferred embodiments of the invention, the pretreated polysiloxanes passes through to poly- silicon
Acquisition is dried in oxygen alkane.
In some embodiments of the invention, the polysiloxanes includes hydroxy-terminated polysiloxane, the end poly- base silicon of hydroxyalkyl
Oxygen alkane, Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorine silicon
One or more of oil and end-vinyl fluorosilicon oil.
In other embodiments of the invention, the modifying agent include the silane modifier containing light-initiated group and/
Or halogenating agent.
In the present invention, the light-initiated group is that the light-initiated group of free radical or cationic photopolymerization cause group.
In some embodiments of the invention, the light-initiated group of the free radical includes acrylate-based and/or acryloyl
Amido.
In other embodiments of the invention, it includes epoxy group, vinyl ether group, benzene that the cationic photopolymerization, which causes group,
It is one or more of in vinyl and sulfydryl vinyl.
In some specific embodiments of the invention, the modified polyorganosiloxane includes the poly- silicon oxygen of acrylate functional
Alkane, acrylamido polysiloxanes, styrenyl polysiloxanes, vinyl ether group polysiloxanes, the poly- silicon of epoxy
One or more of oxygen alkane and sulfydryl vinyl functionalized polysiloxane.
In some embodiments of the invention, in step D, by after casting solution deaeration in substrate knifing.
It in some embodiments of the invention, is 400-1000w for the power of the light source of illumination.
In some embodiments of the invention, the cured time is -3 minutes 30 seconds.
Fourth aspect present invention provides infiltrating and vaporizing membrane or such as third party of the present invention as described in respect of the second aspect of the invention
Application of the infiltrating and vaporizing membrane of the preparation of method described in face in organic solvent to be separated.
In some preferred embodiments of the invention, the organic solvent includes one of butanol, ethyl alcohol and furfural
Or it is several.
Photo-initiated crosslinking infiltrating and vaporizing membrane of the invention it is existing using PDMS as the infiltrating and vaporizing membrane of raw material on the basis of, make
It is poly- with hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl
The not isoplastic polysiloxanes such as siloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end-vinyl fluorosilicon oil, in poly- silicon
Light-initiated group is introduced by the methods of substitution, silanol condensation in oxygen alkane, can obtain saving for a long time based on this, normally
Under the conditions of will not cured casting solution, and be added after photoinitiator carries out knifing on PVDF counterdie, it is certain in certain power
Under the irradiation of the ultraviolet light or visible light of wavelength, the infiltrating and vaporizing membrane that can be fully cured in 1-3min is improved
The infiltrating and vaporizing membrane cured time is substantially reduced while the efficiency of knifing, and after reducing curing time, to a certain extent
Casting solution is prevented to penetrate into the possibility of counterdie, so that separating property is enhanced compared with pure PDMS film.
Detailed description of the invention
To be readily appreciated that the present invention, below in conjunction with attached drawing, the present invention will be described in detail.
Fig. 1 shows the reaction mechanism for preparing modified polyorganosiloxane membrane material.
Fig. 2 shows the reaction mechanisms for preparing modified polyorganosiloxane membrane material.
The reference numerals are as follows in Fig. 1 and Fig. 2: n1、n2And n3For natural number, silicon oxygen in modified polyorganosiloxane is represented
The number of repeat unit of chain；M is natural number, represents the number of repeat unit of modified polyorganosiloxane chain in modified polyorganosiloxane membrane material；R
For light-initiated group contained in modifying agent；R1For polysiloxanes end group；R2For photoinitiator；1 polysiloxanes；2 modifying agent；3 change
Property polysiloxanes；4 modified polyorganosiloxane membrane materials.
Specific embodiment
To keep the present invention easier to understand, it is explained in detail with reference to the accompanying drawings below in conjunction with specific embodiments of the present invention
It is as follows, but be only used as and illustrate and not limit the present invention.
As previously mentioned, it is traditional using polysiloxanes as the curing mode of the preparation process of the infiltrating and vaporizing membrane of raw material be compared with
Rambunctious, after catalyst is added, casting solution is unable to maintain that for a long time, just become in a few minutes it is sticky can not knifing, and
Room temperature or heat cross-linking are generally used after knifing, curing time is longer, it is easy to cause casting solution to penetrate into counterdie, shadow
The separating property of film is rung, this technical bottleneck promote the efficiency of knifing can not, can not carry out continuous knifing, and in room temperature
Under the conditions of be crosslinked if, need a few hours that can just film be made to be fully cured, limit the application of technology in time, for a long time
Solidification so that casting solution penetrates among substrate, affect separating property.In order to solve above-mentioned technical problem, knifing is promoted
Efficiency simultaneously shortens the film fully crosslinked cured time, and the present inventor has carried out largely polysiloxanes membrane material and preparation method thereof
Research.
The present inventor is the study found that introduce light-initiated curing groups on the existing infiltrating and vaporizing membrane using PDMS as raw material
And it is made into casting solution with photoinitiator, obtained casting solution can save for a long time, and the introducing of light substantially reduces infiltration
Vaporization film cured time and the possibility for reducing casting solution infiltration counterdie.The present invention is based on what above-mentioned discovery was made.
Therefore, modified polyorganosiloxane membrane material involved in first aspect present invention is to introduce changing for light-initiated group
Property polysiloxanes be raw material in the presence of photoinitiators through photocuring be made.
In the present invention, the molecular structure of the modified polyorganosiloxane membrane material is as shown in formula I:
In Formulas I,
R is the light-initiated group contained in modifying agent；
R1For polysiloxanes end group comprising terminal hydroxy group, end hydroxyalkyl, Amino End Group, end hydrogen-based, end-vinyl and end chlorine
One or more of base；
R2For photoinitiator；
n1、n2And n3For the number of repeat unit of silicon oxygen chain in modified polyorganosiloxane, value is natural number；
M is the number of repeat unit of modified polyorganosiloxane chain in modified polyorganosiloxane membrane material, and value is natural number.
In the present invention, the photoinitiator is free radical photo-initiation or cation light initiator.
In some embodiments of the invention, the free radical photo-initiation includes but is not limited to 2- hydroxy-2-methyl -1-
Phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, benzoin dimethylether
Deng.
The cation light initiator includes but is not limited to diaryl iodonium salt, triaryl salt compounded of iodine, alkyl salt compounded of iodine, different
Propyl benzene cyclopentadienyl iron hexafluorophosphate etc..
In the present invention, the light-initiated group is that the light-initiated group of free radical or cationic photopolymerization cause group.
In some embodiments of the invention, the light-initiated group of the free radical includes acrylate-based and/or acryloyl
Amido.
In other embodiments of the invention, it includes epoxy group, vinyl ether group, benzene that the cationic photopolymerization, which causes group,
It is one or more of in vinyl and sulfydryl vinyl.
In some embodiments of the invention, the modified polyorganosiloxane membrane material with a thickness of 5-15 μm, contact angle is
103-105°。
Modified polyorganosiloxane membrane material provided by the present invention is a kind of hydrophobic membrane materials, can be used as infiltrating and vaporizing membrane.
Infiltrating and vaporizing membrane involved in second aspect of the present invention includes the poly- silicon oxygen of modification as described in the first aspect of the invention
Alkane membrane material.
In some embodiments of the invention, the infiltrating and vaporizing membrane separates the butanol of 1.5% (v/v) at 45-75 DEG C
The separation factor of aqueous solution is 45-50, flux 700-900L/m2h。
Those skilled in the art will be appreciated that provided by the present invention includes above-mentioned modified polyorganosiloxane membrane material
Infiltrating and vaporizing membrane also can be used in other organic solvents such as separating alcohol, furfural other than it can be used for separating butanol.
Modified polyorganosiloxane membrane material or the infiltration evaporation including the modified polyorganosiloxane membrane material in the present invention
Membrane material is characterized in that solidification process is fully controllable, and curing time is short.
Third aspect present invention provides a kind of preparation method of infiltration evaporation membrane material comprising:
Modified polyorganosiloxane and photoinitiator are mixed and made into casting solution by step C；
Step D, by casting solution, knifing, acquisition are coated on the modified polyorganosiloxane liquid film in substrate in substrate；
Step E solidifies the modified polyorganosiloxane liquid film being coated in substrate under illumination condition, is made containing changing
The infiltrating and vaporizing membrane of property polysiloxanes membrane material.
According to the method for the present invention, the modified polyorganosiloxane is made of by the way that light-initiated group is introduced polysiloxanes.
In certain embodiments of the present invention, the modified polyorganosiloxane is reacted with polysiloxanes by modifying agent by light
Cause group introducing polysiloxanes to be made.
In some preferred embodiments of the invention, the modified polyorganosiloxane is gathered by modifying agent with pretreated
Light-initiated group introducing polysiloxanes is made siloxane reactions.
In some preferred embodiments of the invention, the pretreated polysiloxanes by polysiloxanes into
Row, which is dried, to be obtained.
In some embodiments of the invention, it is described during to be dried include drying, room temperature is dried under reduced pressure and is freeze-dried
One or more, preferably it is described be dried for freeze-drying or room temperature be dried under reduced pressure.
In some preferred embodiments of the invention, the time of the drying is 2-6 hours.
In some embodiments of the invention, the polysiloxanes includes hydroxy-terminated polysiloxane, the end poly- base silicon of hydroxyalkyl
Oxygen alkane, Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorine silicon
One or more of oil and end-vinyl fluorosilicon oil.
In some embodiments of the invention, the modifying agent include the silane modifier containing light-initiated group and/or
Halogenating agent.
The silane modifier containing light-initiated group includes but is not limited to γ-methacryloxypropyl trimethoxy
Base silane, γ-glycidyl ether oxygen propyl trimethoxy silicane etc..
The heretofore described halogenating agent containing light-initiated group, which refers to, can be used as containing for modifying agent of the invention
The halogenated compound of light-initiated group.
The halogenated compound containing light-initiated group includes but is not limited to p-chlorostyrene, acryloyl chloride etc..
The present inventor is further study show that the molecular weight of polysiloxanes will affect the final crosslink density of film, to influence
The infiltration evaporation performance of film.In the present invention weight average molecular weight of polysiloxanes be 10000-100000, preferably 10000-80000,
Further preferably 25000-80000.
In the present invention, the light-initiated group is that the light-initiated group of free radical or cationic photopolymerization cause group.
In some embodiments of the invention, the light-initiated group of the free radical includes acrylate-based and/or acryloyl
Amido.
In other embodiments of the invention, it includes epoxy group, vinyl ether group, benzene that the cationic photopolymerization, which causes group,
It is one or more of in vinyl and sulfydryl-vinyl.
In some specific preferred embodiments of the invention, the modified polyorganosiloxane includes the poly- silicon of acrylate functional
Oxygen alkane, acrylamido polysiloxanes, styrenyl polysiloxanes, vinyl ether group polysiloxanes, epoxy are poly-
One or more of siloxanes and sulfydryl vinyl functionalized polysiloxane.
In some specific preferred embodiments of the invention, prepare modified polyorganosiloxane the following steps are included:
(1) polysiloxanes is carried out dehydrating and obtains pretreated polysiloxanes；
(2) it mixes and reacts with modifying agent again after mixing pretreated polysiloxanes with solvent, be made modified poly-
Siloxanes.
The time of the above-mentioned reaction for preparing modified polyorganosiloxane is 8-12 hours.
The mass ratio of solvent and polysiloxanes is (1-2.5) in above-mentioned steps (2): 1.
The solvent is not particularly limited in the present invention, the solvent is the solvent that can dissolve polysiloxanes,
Including but not limited to acetone, toluene, petroleum ether, ethyl acetate etc..
Substrate is not particularly limited in the present invention, it can be using knifing conventional substrate in this field, for example, described
What substrate can be constituted for non-woven fabrics or other porous support materials or by non-woven fabrics or other porous support materials and ultrafiltration membrane
Composite substrate is directly penetrated into the gap of non-woven fabrics or other porous support materials in order to avoid casting solution, preferably by nonwoven
Knifing is carried out in the composite substrate that cloth or other porous support materials and ultrafiltration membrane are constituted.
Heretofore described composite substrate is a kind of straticulate structure comprising non-woven fabrics or other porous support materials
With the ultrafiltration film layer on a surface for being overlying on non-woven fabrics or other porous support materials layers.Wherein, non-woven fabrics or other porous branch
It timbering material and is overlying on non-woven fabrics or other porous support materials layers only play the role of support, and is overlying on non-woven fabrics or other are porous
The ultrafiltration film layer on one surface of layer of support material is used as counterdie.
Those skilled in the art will be appreciated that either as substrate or still for constituting the nonwoven of composite substrate
Cloth or other porous support materials only play the role of support.
In the present invention, the ultrafiltration film layer as counterdie is hydrophobicity counterdie comprising PVDF (Kynoar) counterdie,
PSF (polysulfones) counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie.
It is easily understood that ought directly on non-woven fabrics or other porous support materials knifing, it is obtained be coated on nothing
After modified polyorganosiloxane liquid film in woven fabric or other porous support materials is cured, be made of reality by non-woven fabrics or its
The straticulate structure of his porous support materials layer and modified polyorganosiloxane membrane layers composition of the invention, also, it is therein
Non-woven fabrics or other porous support materials only play the role of support.
Based on above-mentioned it can be appreciated that when by non-woven fabrics or other porous support materials and being overlying on non-woven fabrics or other are porous
It is obtained coated on compound in the composite substrate that the ultrafiltration film layer (counterdie) on one surface of layer of support material is constituted when knifing
After modified polyorganosiloxane liquid film in substrate is cured, be made of reality by non-woven fabrics or other porous support materials layers,
The straticulate structure that ultrafiltration film layer and modified polyorganosiloxane membrane layers of the invention are constituted；Also, non-woven fabrics therein or
Other porous support materials only play the role of support.And ultrafiltration film layer (mulch) and modified polyorganosiloxane membrane material of the invention
Layer forms structure of composite membrane.
According to the method for the present invention, in the casting solution, ratio of the photoinitiator in casting solution is 0.5wt%-
3wt%.
In some embodiments of the invention, the cured time is -3 minutes 30 seconds, preferably 1-2 minutes.
In the present invention, the light source of used illumination is not particularly limited.However, skilled person should
Solution, the wavelength of illumination is related with photoinitiator, and therefore, knifing is preferably used with power as 400w-1000w in the present invention
The knifing machine of light source is formed by modified polyorganosiloxane liquid film after casting solution attachment and immediately enters light environment, adjusts knifing machine
Speed makes modified polyorganosiloxane liquid film by time of light source be -3 minutes 30 seconds, and preferably 1-2 minute, and in photo-crosslinking solidification
It winds immediately afterwards.
The light source of preferred illumination is ultraviolet light and/or visible light, preferably ultraviolet light in the present invention.
In the present invention, when knifing, does not need in addition to control temperature, this can be understood as knifing and carries out at room temperature.
In some embodiments of the invention, in step D, by after casting solution deaeration in substrate knifing.
In some specific embodiments of the invention, the deaeration includes standing and defoaming and/or vacuum defoamation, preferably
Standing and defoaming.
Those skilled in the art will be appreciated that in step D of the present invention " knifing is carried out in substrate " and step E "
Solidify under illumination condition, infiltration evaporation membrane material be made " although being first to carry out knifing, then carry out photocuring from order of operation
Film forming, but " photocuring " in " knifing " and step E in actually step D is to be carried out continuously and complete.That is, this
Above-mentioned two operation " knifing " and " photocuring " in invention are two steps being carried out continuously.It is prepared and is seeped using the method for the present invention
The continuous operation of knifing and film-forming may be implemented in vaporization film thoroughly.
Photocuring technology is high-efficient, and pollution is few, is a kind of environmental-friendly technology.Certain wavelength ultraviolet light or can
Under light-exposed irradiation, the photoreactive groups that can crosslink polymerization can be divided into two major classes, be the light-initiated group of free radical respectively
And cationic photopolymerization causes group.Wherein the light-initiated group of free radical mainly has acrylate-based and acrylamido, cation
Light-initiated group mainly has epoxy group, vinyl ether group, styryl and sulfydryl-vinyl etc..
Currently, technology of the photocuring in conjunction with polysiloxanes is chiefly used in ink, coating and adhesive, led in UF membrane
Domain is seldom applied, and the present invention combines photocuring technology on the basis of infiltration evaporation film preparation, scrapes membrane efficiency for greatly improving
And shorten curing time.
Light-initiated solidification infiltrating and vaporizing membrane of the invention, with hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, end ammonia
Based polysiloxane, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end ethylene
Base fluorosilicon oil is that raw material compounds to obtain the casting of certain viscosity with photoinitiator by connecting light-initiated group on polysiloxanes
Film liquid, in PVDF (Kynoar) counterdie, PSF (polysulfones) counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie etc.
Film on hydrophobic counterdie is solidified rapidly under conditions of the ultraviolet light of certain wavelength or radiation of visible light, and in nothing
Under conditions of illumination, casting solution can long-term preservation will not solidify.
In the above technical solution, casting solution be acrylate functional polysiloxanes, acrylamido polysiloxanes,
Styrenyl polysiloxanes, vinyl ether group polysiloxanes, epoxy polysiloxanes, sulfydryl vinyl functionalized polysiloxane
Deng.Casting solution synthesizes hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, Amino End Group polysiloxanes, the end poly- silicon of hydrogen-based
Oxygen alkane, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end-vinyl fluorosilicon oil and related group silicon
Alkane modifying agent reacts modified polyorganosiloxane obtained respectively and is mixed to get with photoinitiator.
The reaction mechanism of modified polyorganosiloxane membrane material is prepared in the present invention as shown in Figure 1, passing through photo-initiated crosslinking in Fig. 1
Prepare the method for modified polyorganosiloxane membrane material the following steps are included:
(1) preparation of casting solution: by polysiloxanes 1 (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, Amino End Group
Polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end-vinyl
Fluorosilicon oil) with the silane modifier 2 of corresponding group (substitution reaction) is reacted, modified polyorganosiloxane 3 is made；
(2) photoinitiator is added into modified polyorganosiloxane 3 to stir evenly, casting solution (not shown) is made；Wherein,
Ratio of the photoinitiator in casting solution is 0.5wt%-3wt%；
(3) preparation of infiltrating and vaporizing membrane: after casting solution standing and defoaming, in PVDF (Kynoar) counterdie, PSF (polysulfones)
Knifing on the hydrophobic counterdies such as counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie, knifing are used with power as 400w-
The knifing machine of 1000w ultraviolet lamp (obtains infiltration evaporation liquid film) after casting solution attachment and immediately enters ultraviolet irradiation environment, adjusts
Knifing machine speed makes film by time of ultraviolet lamp be -3 minutes 30 seconds (solidification), and preferably 1-2 minutes, after ultraviolet light irradiation
It winds immediately, obtains the infiltrating and vaporizing membrane of membrane material containing modified polyorganosiloxane 4.
In some specific embodiments of the invention, the preparation method of photo-initiated crosslinking infiltrating and vaporizing membrane of the invention,
The following steps are included:
(1) pretreatment of polymer material: by polysiloxanes (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, end
Amino silicones, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end second
Alkenyl fluorosilicon oil) it is dehydrated in vacuum freeze drier about 2-6 hours, obtain pretreated polysiloxanes.
(2) preparation of casting solution: by pretreated polysiloxanes (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl,
Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end
Vinyl fluoride silicone oil) it is reacted with the silane modifier of corresponding group, modified polyorganosiloxane is made；
(3) photoinitiator is added into modified polyorganosiloxane to stir evenly, casting solution is made, photoinitiator is in casting solution
Ratio be 0.5wt%-3wt%.
(4) preparation of infiltrating and vaporizing membrane: after casting solution standing and defoaming, in PVDF (Kynoar) counterdie, PSF (polysulfones)
Knifing on the hydrophobic counterdies such as counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie, knifing are used with power as 400w-
The knifing machine of 1000w ultraviolet lamp (obtains infiltration evaporation liquid film) after casting solution attachment and immediately enters ultraviolet irradiation environment, adjusts
Knifing machine speed makes film by time of ultraviolet lamp be -3 minutes 30 seconds (solidification), and preferably 1-2 minutes, after ultraviolet light irradiation
It winds immediately, obtains the infiltrating and vaporizing membrane of the membrane material containing modified polyorganosiloxane.
Can be seen that knifing from above-mentioned preparation method and solidify is two steps being carried out continuously, and can be integrated into one
It is carried out in workshop section or step.Preparing infiltrating and vaporizing membrane using the method for the present invention may be implemented the continuous behaviour of knifing and film-forming
Make.
The reaction mechanism of modified polyorganosiloxane membrane material is prepared in the present invention as shown in Fig. 2, passing through photo-initiated crosslinking in Fig. 2
Prepare the method for modified polyorganosiloxane membrane material the following steps are included:
(1) preparation of casting solution: by polysiloxanes 1 (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, Amino End Group
Polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end-vinyl
Fluorosilicon oil) it is reacted with the modifying agent 2 of corresponding group, modified polyorganosiloxane 3 is made；
The modifying agent 2 is silane coupling agent or halogenating agent containing light-initiated group.When the modifying agent 2 be containing
When having the silane coupling agent of light-initiated group, polysiloxanes 1 carries out silanol condensation with the modifying agent 2 of corresponding group and reacts；Work as institute
When to state modifying agent 2 be halogenating agent containing light-initiated group, the modifying agent 2 of polysiloxanes 1 and corresponding group replace anti-
It answers.
(2) photoinitiator is added into modified polyorganosiloxane 3 to stir evenly, casting solution (not shown) is made；Wherein,
Ratio of the photoinitiator in casting solution is 0.5wt%-3wt%；
(3) preparation of infiltrating and vaporizing membrane: after casting solution standing and defoaming, in PVDF (Kynoar) counterdie, PSF (polysulfones)
Knifing on the hydrophobic counterdies such as counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie, knifing are used with power as 400w-
The knifing machine of 1000w ultraviolet lamp (obtains infiltration evaporation liquid film) after casting solution attachment and immediately enters ultraviolet irradiation environment, adjusts
Knifing machine speed makes film by time of ultraviolet lamp be -3 minutes 30 seconds (solidification), and preferably 1-2 minutes, after ultraviolet light irradiation
It winds immediately, obtains the infiltrating and vaporizing membrane of membrane material containing modified polyorganosiloxane 4.
In some specific embodiments of the invention, the preparation method of photo-initiated crosslinking infiltrating and vaporizing membrane of the invention,
The following steps are included:
(1) pretreatment of polymer material: by polysiloxanes (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, end
Amino silicones, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end second
Alkenyl fluorosilicon oil) it is dehydrated in vacuum freeze drier about 2-6 hours, obtain pretreated polysiloxanes.
(2) preparation of casting solution: by pretreated polysiloxanes (hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl,
Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end
Vinyl fluoride silicone oil) it is reacted with the silane modifier 2 of corresponding group, modified polyorganosiloxane is made；
The modifying agent 2 is silane coupling agent or halogenating agent containing light-initiated group.When the modifying agent 2 be containing
When having the silane coupling agent of light-initiated group, polysiloxanes 1 carries out silanol condensation with the modifying agent 2 of corresponding group and reacts；Work as institute
When to state modifying agent 2 be halogenating agent containing light-initiated group, the modifying agent 2 of polysiloxanes 1 and corresponding group replace anti-
It answers.
(3) photoinitiator is added into modified polyorganosiloxane to stir evenly, casting solution is made, photoinitiator is in casting solution
Ratio be 0.5wt%-3wt%.
(4) preparation of infiltrating and vaporizing membrane: after casting solution standing and defoaming, in PVDF (Kynoar) counterdie, PSF (polysulfones)
Knifing on the hydrophobic counterdies such as counterdie, PES (polyether sulfone) counterdie, PS (polystyrene) counterdie, knifing are used with power as 400w-
The knifing machine of 1000w ultraviolet lamp (obtains infiltration evaporation liquid film) after casting solution attachment and immediately enters ultraviolet irradiation environment, adjusts
Knifing machine speed makes film by time of ultraviolet lamp be -3 minutes 30 seconds (solidification), and preferably 1-2 minutes, after ultraviolet light irradiation
It winds immediately, obtains the infiltrating and vaporizing membrane of the membrane material containing modified polyorganosiloxane.
Can be seen that knifing from above-mentioned preparation method and solidify is two steps being carried out continuously, and can be integrated into one
It is carried out in workshop section or step.Preparing infiltrating and vaporizing membrane using the method for the present invention may be implemented the continuous behaviour of knifing and film-forming
Make.
Heretofore described term " winding " refers to the method for batching this continuous product of film with reel.
Heretofore described " water " word refers to deionized water, distilled water under conditions of being not particularly illustrated or limiting
Or ultrapure water.
The present invention introduces photocuring technology in the preparation of infiltrating and vaporizing membrane, connects in wide variety of silicone light-initiated solid
Change group and be made into casting solution with photoinitiator, obtained casting solution can save for a long time, and the introducing of light substantially reduces
Infiltrating and vaporizing membrane cured time and the possibility for reducing casting solution infiltration substrate.
Further, the present invention using hydroxy-terminated polysiloxane, the poly- radical siloxane of end hydroxyalkyl, Amino End Group polysiloxanes,
Hold hydrogen-based polysiloxanes, end-vinyl polysiloxanes, end chloro polysiloxanes, terminal hydroxy group fluorosilicon oil, end-vinyl fluorosilicon oil with
Related group silane modifier reacts respectively obtains acrylate functional polysiloxanes, acrylamido polysiloxanes, benzene second
Alkenyl polysiloxanes, vinyl ether group polysiloxanes, epoxy polysiloxanes, sulfydryl vinyl functionalized polysiloxane etc. change
Property polysiloxanes, the casting solution that modified polysiloxanes and photoinitiator are mixed knifing and in certain function in substrate
Solidified under the light irradiation of the certain wavelength of rate, obtains the infiltrating and vaporizing membrane containing photo-crosslinking modified polyorganosiloxane membrane material.
Embodiment
Embodiment 1:
(1) in the three-necked flask for having blender, thermometer, reflux condensing tube, the hydroxyl for being separately added into 10-35% is poly-
Siloxanes (counterpoise quality 10000-80000), the toluene of 55-80%, the isocyanates of 0.1-1%, 0.01-0.05% go from
The DBTDL (dibutyl tin dilaurate) of sub- water, 0.02-0.1%, successive reaction 6-12 hours at 80-100 DEG C, reaction terminates
Vacuum distillation removes toluene, water etc. afterwards, obtains the performed polymer (modified polyorganosiloxane) of styrenyl polysiloxanes.
(2) two virtue of cation light initiator of 0.5-3% is added in styrene performed polymer (modified polyorganosiloxane) solution
Base salt compounded of iodine I-250, obtains casting solution after mixing evenly.
(3) opening UV crosslinking instrument stablizes electric current, a certain amount of casting solution is added in hopper, adjusting scraper distance is
Automatic knifing machine is opened after 40 μm, knifing is carried out on PSF counterdie with the speed of 0.5-1m/min, so that film passes through ultraviolet lamp
Time is about 1-3min, is fully cured by ultraviolet lamp caudacoria, knifing machine automatic winding, obtains styrenyl polysiloxanes infiltration
Vaporization film thoroughly.
(4) the infiltrating and vaporizing membrane film thickness obtained is 5-15 μm, and contact angle is 103-105 °, separates 1.5% at 45-75 DEG C
Butanol aqueous solution, separation factor 45-50%, flux 700-900L/m2h。
Embodiment 2:
(1) in the three-necked flask for having blender, thermometer, reflux condensing tube, the hydroxyl for being separately added into 10-35% is poly-
Siloxanes (counterpoise quality 25000-80000), the toluene of 55-80%, 0.1-1% KH-570 (γ-methacryloxy third
Base trimethoxy silane), the deionized water of 0.01-0.05%, 0.02-0.1% DBTDL (dibutyl tin dilaurate), 80-
Successive reaction 6-12 hours at 100 DEG C, vacuum distillation removes toluene, water etc. after reaction, obtains the poly- silicon of acrylate functional
The performed polymer of oxygen alkane.
(2) free radical photo-initiation TPO-L (the 2,4,6- front three of 0.5-3% is added in acrylate prepolymer body solution
Base benzoyl phosphinic acid ethyl ester), casting solution is obtained after mixing evenly.
(3) opening UV crosslinking instrument stablizes electric current, a certain amount of casting solution is added in hopper, adjusting scraper distance is
Automatic knifing machine is opened after 40 μm, knifing is carried out on PES counterdie with the speed of 0.5-1m/min, so that film passes through ultraviolet lamp
Time is about 1-3min, is fully cured by ultraviolet lamp caudacoria, and knifing machine automatic winding obtains acrylate functional polysiloxanes
Infiltrating and vaporizing membrane.
(4) the infiltrating and vaporizing membrane film thickness obtained is 10-15 μm, and contact angle is 103-105 °, is separated at 45-75 DEG C
1.5% butanol aqueous solution, separation factor 45-50%, flux 700-900L/m2h。
Embodiment 3:
(1) in the three-necked flask for having blender, thermometer, reflux condensing tube, it is separately added into the end chloro of 10-35%
Polysiloxanes (counterpoise quality 25000-80000), the toluene of 55-80%, 0.1-1% silicon Acrylote alcohol ester, 0.01-0.05%
Deionized water, 0.02-0.1% DBTDL (dibutyl tin dilaurate), successive reaction 6-12 hours at 80-100 DEG C, instead
Vacuum distillation removes toluene, water etc. after answering, and obtains the performed polymer of acrylate functional polysiloxanes.
(2) the cation light initiator diaryl iodonium salt I- of 0.5-3% is added in acrylate prepolymer body solution
250, casting solution is obtained after mixing evenly.
(3) opening UV crosslinking instrument stablizes electric current, a certain amount of casting solution is added in hopper, adjusting scraper distance is
Automatic knifing machine is opened after 40 μm, knifing is carried out on PVDF counterdie with the speed of 0.5-1m/min, so that film passes through ultraviolet lamp
Time be about 30s-3min, preferably 1-2min is fully cured by ultraviolet lamp caudacoria, and knifing machine automatic winding obtains benzene second
Alkenyl polysiloxanes infiltrating and vaporizing membrane.
(4) the infiltrating and vaporizing membrane film thickness obtained is 10-15 μm, and contact angle is 103-105 °, is separated at 45-75 DEG C
1.5% butanol aqueous solution, separation factor 45-50%, flux 700-800L/m2h。
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of modified polyorganosiloxane membrane material, shown in molecular structure such as formula (I):
In formula (I),
R is light-initiated group contained in modifying agent；
R1For polysiloxanes end group；
R2For photoinitiator；
n1、n2And n3For the number of repeat unit of silicon oxygen chain in modified polyorganosiloxane, value is natural number；
M is the number of repeat unit of modified polyorganosiloxane chain in modified polyorganosiloxane membrane material, and value is natural number.
2. modified polyorganosiloxane membrane material according to claim 1, which is characterized in that the modified polyorganosiloxane membrane material
With a thickness of 5-15 μm, contact angle is 103-105 °.
3. a kind of infiltrating and vaporizing membrane comprising modified polyorganosiloxane membrane material as claimed in claim 1 or 2, it is preferable that described
The separation factor that infiltrating and vaporizing membrane separates the butanol aqueous solution of 1.5% (v/v) at 45-75 DEG C is 45-50, flux 700-
900L/m2h。
4. a kind of preparation method of infiltrating and vaporizing membrane comprising:
Modified polyorganosiloxane and photoinitiator are mixed and made into casting solution by step C；
Step D, by casting solution, knifing, acquisition are coated on the modified polyorganosiloxane liquid film in substrate in substrate；
Step E solidifies the modified polyorganosiloxane liquid film being coated in substrate under illumination condition, is made containing modified poly-
The infiltrating and vaporizing membrane of silicone film material.
5. according to the method described in claim 4, it is characterized in that, the modified polyorganosiloxane is by drawing light-initiated group
Enter polysiloxanes to be made；Gather it is preferred that the modified polyorganosiloxane reacts to introduce light-initiated group with polysiloxanes by modifying agent
Siloxanes is made；The further preferred modified polyorganosiloxane, which is reacted by modifying agent with pretreated polysiloxanes, draws light
Hair group introduces polysiloxanes and is made.
6. method according to claim 4 or 5, which is characterized in that the polysiloxanes includes hydroxy-terminated polysiloxane, end
The poly- radical siloxane of hydroxyalkyl, Amino End Group polysiloxanes, end hydrogen-based polysiloxanes, end-vinyl polysiloxanes, the end poly- silicon oxygen of chloro
One or more of alkane, terminal hydroxy group fluorosilicon oil and end-vinyl fluorosilicon oil；And/or the modifying agent includes containing light-initiated
The silane modifier and/or halogenating agent of group；And/or the light-initiated group is the light-initiated group of free radical or cation
Light-initiated group；It is preferred that the light-initiated group of free radical includes acrylate-based and/or acrylamido；It is preferred that it is described sun from
It includes one or more of in epoxy group, vinyl ether group, styryl and sulfydryl vinyl that sub-light, which causes group,.
7. method according to claim 5 or 6, which is characterized in that the modified polyorganosiloxane includes acrylate functional
Polysiloxanes, acrylamido polysiloxanes, styrenyl polysiloxanes, vinyl ether group polysiloxanes, epoxy group
Change one or more of polysiloxanes and sulfydryl vinyl functionalized polysiloxane.
8. the method according to any one of claim 4-7, which is characterized in that the pretreated polysiloxanes is logical
It crosses and acquisition is dried to polysiloxanes；And/or in step D, by after casting solution deaeration in substrate knifing.
9. the method according to any one of claim 3-7, which is characterized in that the power of the light source for illumination is
400-1000w；And/or the cured time is -3 minutes 30 seconds.
10. infiltrating and vaporizing membrane as claimed in claim 3 or the infiltration of the method preparation as described in any one of claim 4-9
Application of the vaporization film in organic solvent to be separated thoroughly；It is preferred that the organic solvent includes one of butanol, ethyl alcohol and furfural
Or it is several.
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