CN1339523A - Film surface light grafting by dynamic method - Google Patents
Film surface light grafting by dynamic method Download PDFInfo
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- CN1339523A CN1339523A CN 01141434 CN01141434A CN1339523A CN 1339523 A CN1339523 A CN 1339523A CN 01141434 CN01141434 CN 01141434 CN 01141434 A CN01141434 A CN 01141434A CN 1339523 A CN1339523 A CN 1339523A
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Abstract
The present invention modifies film surface through dynamic light grafting process. Initiator or its mixture with monomer is first irradiated by ultraviolet ray to produce initiator free radical. Initiator or its mixture with monomer is then pumped by pump or air pressure to the surface of film and made to penetrate the film to produce light grafting. It case of sole conveyance of the initiator, the light grafting the completed through two steps of conveying initiator and conveying monomer after washing out excessive initiator.
Description
The present invention relates to film surface light grafting method, particularly adopt dynamic method to carry out the surface light grafting, promptly under pump or the air pressure or under the suction function, allow the while such as initiator, monomer or in succession infiltration, percolation cross film, in this process, finish the photo-grafting reaction.
The groundwork of ultraviolet radiation graft technology aspect separatory membrane at present has: 1) enzyme, sorbent material, catalyzer etc. are in the immobilization on film surface; 2) prepare separatory membrane with memory function; 3) preparation is by the separatory membrane of envrionment conditions control performance; There are two big shortcoming in above-mentioned work: 1) all ultraviolet surface light grafting all are can carry out according to the part of seeing in UV-light, and ultraviolet lighting is not
The part that arrives, as the film of tubular fibre inside, interior pressure-pipe type film inside, rolled film inside and film
The grafting problem of sorting hole inside can't solve with aforesaid method.2) static state: all at present research work all are by UV-irradiation, monomer polymerization, remove not polymerization
Steps such as monomer are formed.Be that monomer or initiator all are relative immobilized with film, in grafting
Do not have the relative movement of initiator, monomer etc. and film in the whole process, promptly do not have initiator and monomer
The working cycle that infiltration, percolation are crossed film.
Industrial general be used tubular fibre, rolled film etc. more and more on a large scale.Produce, the needs of life, require to illumination less than place (light blind area) carry out the surface light graft modification.
Task of the present invention provides a kind of method, makes the visible light part of film and lose the light part to carry out the surface light grafting.
The present invention finishes as follows: initiator separately or initiator and monomeric mixture be placed under the UV-light and shine, make initiator produce free radical, again initiator or initiator and monomeric mixture with pump or air pressure or under suction function, be transported to the film surface, make it pass film, in this process, carry out the photo-grafting reaction, under the situation that initiator is carried separately, after carrying initiator, the flush away residual initiators is carried monomer again, finishes photo-grafting by two steps and reacts.
The invention provides 4 in accompanying drawing, wherein:
Fig. 1 is the dynamic gas-phase reaction device of UV-light surface light grafting
Fig. 2 is the dynamic gas-phase reaction device of two step method UV-light surface light grafting
Fig. 3 is the dynamic liquid-phase reaction system of ultraviolet radiation graft
Fig. 4 is the dynamic liquid-phase reaction system of two step method ultraviolet radiation graft
Below in conjunction with accompanying drawing invention is further described.
Embodiment one
The dynamic gas-phase reaction device of UV-light surface light grafting as shown in Figure 1, it is made up of ultraviolet lamp [1], silica glass cover plate [2], baffle plate [3], reaction tank seal cover board [4], sealing-ring [5], matrix membrane [6], porous supporting plate [7], reaction tank [8], reaction liquid bath [9], reaction chamber [10], vacuum unit interface [11].With sealing between silica glass cover plate [2] and reaction chamber [10], connect vacuum extractor at vacuum unit interface [11].Photosensitizers both can be coated on the matrix membrane [6], can be blended in the solution of reaction liquid bath [9] with monomer again.In the reaction liquid bath [9] can be monomer solution, also can be photosensitizers and monomeric mixing solutions.Heating makes the solution evaporation in the reaction liquid bath [9].When system is subjected to UV-irradiation, photosensitizers steam produces free radical, itself and solvent vapo(u)r and monomer vapours are passed matrix membrane [6] under the suction function of vacuum extractor, photosensitizers and the film generation surface free radical that reacts in this process, and then trigger monomer at the lip-deep graft reaction of film.
Embodiment two
The dynamic gas-phase reaction device of two step method UV-light surface light grafting as shown in Figure 2, it is made up of ultraviolet lamp [1], silica glass cover plate [2], baffle plate [3], reaction tank seal cover board [4], sealing-ring [5], matrix membrane [6], porous supporting plate [7], reaction tank [8], reaction chamber [10], vacuum unit interface [11], photosensitizers vaporizer [13], photosensitizers groove [9], monomer vaporizer [14], monomer liquid bath [12], three-way valve [15].With sealing between silica glass cover plate [2] and reaction chamber [10], connect vacuum extractor at vacuum unit interface [11], reaction chamber is transferred to suitable temperature.Regulate three-way valve [15], reaction chamber [10] is communicated with photosensitizers vaporizer [13], heating makes the solution evaporation in the photosensitizers groove [9].When system was subjected to UV-irradiation, photosensitizers steam produced free radical, and itself and solvent vapo(u)r pass matrix membrane [6] under the suction function of vacuum extractor, photosensitizers and the film generation surface free radical that reacts in this process.
Through behind the certain hour, regulate three-way valve [15], reaction chamber [10] is communicated with monomer vaporizer [14], heating makes the solution evaporation in the monomer liquid bath [12], monomer vapours and solvent vapo(u)r pass film [6] under the suction function of vacuum extractor, and with film on the surface free radical generation graft reaction that existed.
Also can be without T-valve [15], and connect monomer vaporizer [14] and photosensitizers vaporizer [13] respectively with two two-way valves.Can also directly be coated onto photosensitizers on the matrix membrane [6], save the photosensitizers vaporizer, only stay the monomer vaporizer.Baffle plate [3] also can omit in this device in addition.
Embodiment three
The dynamic liquid-phase reaction system of ultraviolet radiation graft as shown in Figure 3, it by ultraviolet lamp [10], silica glass cover plate [9], irrigant stream inlet [12], irrigant stream outlet [7], nitrogen feed mouthful [2], a nitrogen relief outlet [3], filling tube [1], flushing chamber [8], reaction liquid chamber [4], membrane carrier [6], flange [5] is formed.
To seal between silica glass cover plate [9] and the flushing chamber [8], in reaction liquid chamber [4], feed nitrogen and protect, on reaction liquid chamber [4], apply the temperature regulation measure.Photosensitizers can be coated on the membrane carrier [6], also can be made into reaction solution with monomer, and clean-out system influx [12], clean-out system spout [7] are connected on the two ends of flushing pump respectively.Both can provide power for reaction solution [11] sees through membrane carrier [6] by flowing of irrigation, the reaction solution that can take away through film prevents homopolymerization again.Under the irradiation of ultraviolet lamp [10], photosensitizers produces free radical on the surface of membrane carrier, and dynamic photo-grafting reaction takes place in the saturating membrane process of reaction solution.
Also can be with photosensitizers, clean-out system and monomer difference wiring solution-forming, add photosensitizers solution earlier by filling tube [1], treat that photosensitizers solution is all through adding detergent solution again behind the membrane carrier [6], the photosensitizers that flush away is unnecessary, agent solution to be cleaned adds monomer solution again and carries out graft reaction after seeing through membrane carrier [6].
Embodiment four
4，[13]、[12]、[17]、[16]、[11]、[7][8][10]、[9]、[25]、[32]、[15]、[23]、[30]、[20]、[27]、[34]、[14]、[22]、[29]、[18]、[24]、[31]、[1]、[2]、[3]、[4]、[5]、[6]、[21]、[28]、[35]。
To seal between silica glass cover plate [16] and the photosensitizers groove [17], in each groove, feed nitrogen and protect, each groove and membrane module and between pipeline on all add temperature and regulate measure.Photosensitizers solution [19] reacts under the irradiation of ultraviolet lamp [13], produces free radical.Valve [3], [6], [21] are opened in closing valve [1], [2], [4], [5], [28], [35].Under the effect of pump [11], photosensitizers free-atom aqueous solution [19] is flowed out by spout [20], by membrane module [9], free radical is transferred to the film surface, form surface free radical, get back in the photosensitizers groove [17] via influx [15], finish circulation by the photosensitizers solution of membrane module [9].
Through behind the certain hour, valve [2], [5], [28] are opened in closing valve [1], [3], [4], [6], [21], [35].Wash unnecessary photosensitizers free radical with scavenging solution [26] off through spout [27].Scavenging solution flows back in the cleaning liquid bath [25] via influx [23] by behind the membrane module [9], finishes circulation.
Behind the certain hour, valve [1], [4], [35] are opened in closing valve [2], [3], [5], [6], [21], [28], and under the effect of pump [11], monomer solution [33] is via spout [34], by membrane module [9].The free radical reaction on monomer molecule and film surface is carried out photo-grafting, and monomer solution flows back in the monomer liquid bath [32] via influx [30] by behind the membrane module [9], finishes circulation.
For preventing mixing mutually between photosensitizers, monomer and the washing composition, also each groove can be divided into two chambers, circulation is flowed back to liquid separates in liquid and the former groove.Both can flow back to former liquid bath from the tube side of membrane module and the effluent liquid of shell side in addition, also can flow back to former liquid bath from independent separately influx respectively from a common influx.
Claims (5)
1, a kind of film surface light grafting method, it is characterized in that carrying out the surface light grafting with dynamic method, initiator separately or initiator and monomeric mixture be placed under the UV-light and shine, make initiator produce free radical, again initiator or initiator and monomeric mixture with pump or air pressure or under suction function, be transported to the film surface, make it pass film, in this process, carry out the photo-grafting reaction, under the situation that initiator is carried separately, after carrying initiator, the flush away residual initiators is carried monomer again, finishes photo-grafting by two steps and reacts.
2, method by claim 1 regulation, it is characterized in that the dynamic gas-phase reaction device of UV-light surface light grafting is by ultraviolet lamp [1], silica glass cover plate [2], baffle plate [3], reaction tank seal cover board [4], sealing-ring [5], matrix membrane [6], porous supporting plate [7], reaction tank [8], reaction liquid bath [9], reaction chamber [10], vacuum unit interface [11] is formed, to seal between silica glass cover plate [2] and reaction chamber [10], connect vacuum extractor at vacuum unit interface [11], photosensitizers both can be coated on the matrix membrane [6], can be blended in the solution of reaction liquid bath [9] with monomer again, in the reaction liquid bath [9] can be monomer solution, also can be photosensitizers and monomeric mixing solutions, heating makes the solution evaporation in the reaction liquid bath [9], when system is subjected to UV-irradiation, photosensitizers steam produces free radical, itself and solvent vapo(u)r and monomer vapours are passed matrix membrane [6] under the suction function of vacuum extractor, photosensitizers and the film generation surface free radical that reacts in this process, and then trigger monomer at the lip-deep graft reaction of film.
3, method by claim 1 regulation, it is characterized in that the dynamic gas-phase reaction device of two step method UV-light surface light grafting is by ultraviolet lamp [1], silica glass cover plate [2], baffle plate [3], reaction tank seal cover board [4], sealing-ring [5], matrix membrane [6], porous supporting plate [7], reaction tank [8], reaction chamber [10], vacuum unit interface [11], photosensitizers vaporizer [13], photosensitizers groove [9], monomer vaporizer [14], monomer liquid bath [12], three-way valve [15] is formed, to seal between silica glass cover plate [2] and reaction chamber [10], connect vacuum extractor at vacuum unit interface [11], reaction chamber is transferred to suitable temperature, regulate three-way valve [15], reaction chamber [10] is communicated with photosensitizers vaporizer [13], heating makes the solution evaporation in the photosensitizers groove [9], when system is subjected to UV-irradiation, free radical and solvent vapo(u)r that photosensitizers steam produces pass matrix membrane [6] under the suction function of vacuum extractor, photosensitizers and the film generation surface free radical that reacts in this process, through behind the certain hour, regulate three-way valve [15], reaction chamber [10] is communicated with monomer vaporizer [14], heating makes the solution evaporation in the monomer liquid bath [12], monomer vapours and solvent vapo(u)r pass film [6] under the suction function of vacuum extractor, and with film on the surface free radical generation graft reaction that existed, also can be without T-valve [15], and connect monomer vaporizer [14] and photosensitizers vaporizer [13] respectively with two two-way valves, can also directly be coated onto photosensitizers on the matrix membrane [6], save the photosensitizers vaporizer, only stay the monomer vaporizer, baffle plate [3] also can omit in this device in addition.
4; method by claim 1 regulation; it is characterized in that the dynamic liquid-phase reaction system of ultraviolet radiation graft is by ultraviolet lamp [10]; silica glass cover plate [9]; irrigant stream inlet [12]; irrigant stream outlet [7]; nitrogen feeds mouthful [2]; nitrogen relief outlet [3]; filling tube [1]; flushing chamber [8]; reaction liquid chamber [4]; membrane carrier [6]; flange [5] is formed; to seal between silica glass cover plate [9] and the flushing chamber [8]; feeding nitrogen in reaction liquid chamber [4] protects; go up the installation temperature control equipment at reaction liquid chamber [4]; photosensitizers can be coated on the membrane carrier [6]; also can be made into reaction solution with monomer; irrigant stream inlet [12]; irrigant stream outlet [7] is connected on the two ends of flushing pump respectively; for seeing through membrane carrier [6], reaction solution [11] provides power by flowing of irrigation; take away the reaction solution that sees through film and prevent homopolymerization; under the irradiation of ultraviolet lamp [10]; the free radical that photosensitizers produces on the surface of membrane carrier; in the saturating membrane process of reaction solution, cause the photo-grafting reaction; also can be with photosensitizers; clean-out system and monomer be wiring solution-forming respectively; add photosensitizers solution earlier by filling tube [1]; treat that photosensitizers solution is all through adding detergent solution again behind the membrane carrier [6]; the photosensitizers that flush away is unnecessary adds monomer solution again and carries out graft reaction.
5; method by claim 1 regulation; it is characterized in that the dynamic liquid-phase reaction system of two step method ultraviolet radiation graft is by ultraviolet lamp [13]; reflective mirror [12]; photosensitizers groove [17]; silica glass cover plate [16]; pump [11]; tensimeter [7]; [8]; [10]; membrane module [9]; washing composition groove [25]; monomer liquid bath [32]; liquid flow inlet [15]; [23]; [30]; liquid flowing outlet [20]; [27]; [34]; nitrogen feeds mouthful [14]; [22]; [29]; nitrogen relief outlet [18]; [24]; [31]; valve [1]; [2]; [3]; [4]; [5]; [6]; [21]; [28]; [35] form; to seal between silica glass cover plate [16] and the photosensitizers groove [17]; feeding nitrogen in each groove protects; each groove and membrane module and between pipeline on temperature control equipment all is installed; closing valve [1]; [2]; [4]; [5]; [28]; [35]; open valve [3]; [6]; [21]; under the effect of pump [11]; photosensitizers free-atom aqueous solution [19] is flowed out by spout [20]; by membrane module [9]; the film surface is arrived in radical transfer; photosensitizers solution by membrane module [9] is got back in the photosensitizers groove [17] via influx [15]; finish circulation; through behind the certain hour; closing valve [1]; [3]; [4]; [6]; [21]; [35]; open valve [2]; [5]; [28]; wash unnecessary photosensitizers free radical with washings [26] off through spout [27]; washings is by behind the membrane module [9]; flow back in the washing liquid bath [25] via influx [23]; finish circulation; through behind the certain hour; closing valve [1]; [3]; [4]; [6]; [21]; [35]; open valve [2]; [5]; [28]; wash unnecessary photosensitizers free radical with scavenging solution [26] off through spout [27]; scavenging solution is by behind the membrane module [9]; flow back in the washing liquid bath [25] via influx [23]; finish circulation; behind the certain hour; closing valve [2]; [3]; [5]; [6]; [21]; [28]; open valve [1]; [4]; [35]; under the effect of pump [11]; monomer solution [33] is via spout [34]; by membrane module [9]; monomer solution is by behind the membrane module [9]; flow back in the monomer liquid bath [32] via influx [30]; finish circulation; for preventing photosensitizers; mixing mutually between monomer and the washing composition; also each groove can be divided into two chambers; circulation flowed back to liquid separates in liquid and the former groove; circulation fluid and see through liquid and both can flow back to former liquid bath from a common influx also can flow back to former liquid bath from independent separately influx respectively in addition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01141434 CN1339523A (en) | 2001-09-25 | 2001-09-25 | Film surface light grafting by dynamic method |
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| CN 01141434 CN1339523A (en) | 2001-09-25 | 2001-09-25 | Film surface light grafting by dynamic method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299810C (en) * | 2003-11-03 | 2007-02-14 | 浙江大学 | Method for modifying hydroophilicity of highly active separation membrane made from polymer |
| CN108586790A (en) * | 2018-04-11 | 2018-09-28 | 哈尔滨理工大学 | A kind of polymeric U light irradiation grafting experimental provision |
-
2001
- 2001-09-25 CN CN 01141434 patent/CN1339523A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299810C (en) * | 2003-11-03 | 2007-02-14 | 浙江大学 | Method for modifying hydroophilicity of highly active separation membrane made from polymer |
| CN108586790A (en) * | 2018-04-11 | 2018-09-28 | 哈尔滨理工大学 | A kind of polymeric U light irradiation grafting experimental provision |
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