CN101318119B - Novel polymer based microfluid reactor suitable for photochemistry reaction and preparation method thereof - Google Patents
Novel polymer based microfluid reactor suitable for photochemistry reaction and preparation method thereof Download PDFInfo
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- CN101318119B CN101318119B CN2008101137773A CN200810113777A CN101318119B CN 101318119 B CN101318119 B CN 101318119B CN 2008101137773 A CN2008101137773 A CN 2008101137773A CN 200810113777 A CN200810113777 A CN 200810113777A CN 101318119 B CN101318119 B CN 101318119B
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Abstract
The invention relates to a novel polymer-based microfluid reactor applicable to photochemical reaction and the preparation method thereof and belongs to the technical field of the manufacture of the polymer-based microfluid reactor. The preparation method of the reactor comprises: manufacturing a screwed hole with a non-breakthrough top used for connecting external equipment on the inlet and outlet position of a PMMA base; spin coating an EA51 glue layer on the surface of the PMMA for modifying the surface; spin coating an SU8 glue layer on the surface of the EA51 glue layer and carrying out three steps of processes of pre-baking, exposing and post-braking; developing the unexposed part of the SU8 glue layer to form a micro channel pattern; getting through the inlet and the outlet; spin coating an EA51 glue layer on the surface of a BOPP membrane which goes through hydroxylation treatment to form a sealing glue layer; sealing the micro channel pattern; exposing the top sealing layer under close compaction state to lead to complete solidification of the glue layer; thus forming the closed micro channel; screwing the PEEK bolt of an internal tight tube into the screwed hole. The reactor, which is an all-organic transparent microfluid reactor, solves the common problems in the manufacture of the current microfluid reactor and realizes lighting synthesis of nano-particles and polymer microsphere and the like particles.
Description
Technical field:
The invention belongs to polymer based microfluid reactor manufacturing technology field, and with the method for this micro-fluid reactor controlledly synthesis micron and nano particle.
Background technology:
Theory based on parallel processing and parallel amplification; micro-fluid reactor can directly be amplified to the large-scale production stage and needn't consider enlarge-effect from conceptual phase; but the physical and chemical performance of finely regulating final products is demonstrating increasing potentiality aspect the purity of low consumption high production, raising product simultaneously.By efficient, controllability and the reduction raw material consumption that improves chemical reaction, micro-fluid reactor can be reduced to environment intrinsic in the conventional batch reaction and healthy prestige danger minimum, as avoid large-scale transportation and store potential blast, the leakage of poisonous substance and combustibles etc.In addition, compare with traditional chemical technology, micro-fluid reactor can be controlled at reaction volume to receive and rise or littler volume, and to the chemical reaction of reactant costliness, its research cost can reduce significantly; Can parallelly carry out simultaneously extensive sample reaction and obtain large result; Because its little reaction volume, its mass transfer and heat transfer efficiency are very high.Therefore, micro fluid reaction technology is an environmental protection, energy-conservation, efficient, the chemical reaction technology of supporting cost.
At present, the manufacturing of micro-fluid reactor also exists some obstacles, as utilize the expensive problem of existing mould pressing technology preparation feedback device, be difficult to prepare the runner of small size and high-aspect-ratio, have the sealing of flow passage system and the problems such as compatibility between resistance to pressure and reactor structure material and reactant.The structure material that micro-fluid reactor is used always comprises various metals, stainless steel, and silicon chip, borosilicate glass, its preparation technology follows the photoengraving technology of tediously long costliness usually.And these technologies can't realize deep reactive ion etching (DRIE), thereby are unfavorable for preparing the high-aspect-ratio fluid channel, reduce fluid pressure drop, improve productive rate.
Utilizing polymer to make micro-fluid reactor can effectively reduce cost, and simplifies technology, enhances productivity.Yet still need solve three subject matters: the first, the capping of microfluidic channel realizes clog-free, firm connection and enough printing opacities; The second, the chemically compatible modification of matrix and with the firm bonding of fluid channel pattern; The 3rd, the hydrophile-lipophile balance modification of micro polymer fluid passage inwall.
SU8 has high-aspect-ratio and the vertical characteristics of sidewall, often is applied to make the micro-structural of electroplating mold, various high-aspect-ratios, as micropin, microtrabeculae etc., or makes deep trench on chip, and as the masterplate of other polymer base micro-structural.Because its excellent biological compatibility, resistance to acids and bases and anti-causticity solvent borne, little processing is simple, and is good with silicon processing technology compatibility, and SU8 becomes one of material commonly used in the microfluid making in recent years.Based on the standard silicon processing technology, utilize SU8, polymethyl methacrylate (PMMA), Merlon (PC) and dimethyl silicone polymer (PDMS) all can prepare the microchannel structure of complexity, multilayer.And compare with common PDMS, PMMA, SU8 is more suitable for preparing the fluid channel of high-aspect-ratio.Yet, utilize SU8 to prepare micro-fluid reactor and still need face following difficulty: the first, also do not have a kind of inexpensive method that SU8 is carried out capping, and realize not having and stop up, and the top light transmission of fluid channel.U.S.Pat.No.2006/0014271A (Yujun Song, Challa Kumar, Josef Hormes.Fabrication of a completely polymericmicrofluidic reactor for chemical synthesis[P] .US Patent, US 2006/0014271 A1.2004-07-16) described in a kind of SU8 of utilization thin adhesive layer succinct, " the semi-solid transfer " capping method, but this method can't make the top printing opacity, limited photochemically reactive possibility, SU8 is higher as the cover closing material cost simultaneously; The second, SU8 is a hydrophobic material, and microchannel need carry out the hydrophile-lipophile balance modification and fall and the wall pollution with the pressure that reduces runner, is applicable to the reaction of different solvents system.
Summary of the invention:
The present invention seeks to have proposed a kind of quick manufacturing polymer based microfluid reactor and method thereof, and with the microfluid technology of it controlled preparation nanometer and micron particles.
The invention provides a kind of photochemically reactive polymer based microfluid reactor that is suitable for, it is characterized in that, comprise successively from bottom to up:
Importing and exporting the matrix that the position has the PMMA of screwed hole, be screwed into the be locked PEEK screw of conduit of inside in this screwed hole, this conduit outlet is fixed on the bottom of import and export;
The EA51 glue-line of PMMA matrix surface spin coating;
At the SU8 glue-line of EA51 glue-line surface spin coating, this SU8 glue-line unexposed portion develops and forms the fluid channel pattern;
The capping glue-line that BOPP film surface spin coating one deck EA51 glue-line of handling in hydroxylating forms, this capping glue-line carries out capping to the SU8 glue-line fluid channel pattern that opens wide.
The preparation method of above-mentioned reactor is characterized in that, may further comprise the steps:
A: process the screwed hole that the top that is connected with external equipment is not got through in the import and export position of PMMA matrix;
B:, carry out surface modification at the matrix PMMA of cleaning surface spin coating one deck EA51 glue-line;
C:, and carry out preceding baking, exposure and back baking three step process at EA51 glue-line surface spin coating SU8 glue-line;
D: then SU8 glue-line unexposed portion is developed, form the fluid channel pattern;
E: get through all import and export;
F: BOPP film surface spin coating one deck EA51 glue-line of handling in hydroxylating forms the capping glue-line; And the capping glue-line carried out pre-exposure, and make the partial cross-linked curing of glue-line, be semisolid;
G; The fluid channel pattern that opens wide is carried out capping, and exposure is solidified glue-line fully to the top closure layer under tightly compacted state, has just formed the microchannel of sealing.
H: the be locked PEEK screw of conduit of inside is screwed into screwed hole, makes conduit outlet be fixed on the bottom of import and export.
Hydroxylating in the described step F is treated to:
The ammonium persulfate aqueous solution of configuration 15%-30%wt, drip this ammonium persulfate aqueous solution between the BOPP of two cleanings film, two BOPP films that accompany ammonium persulfate solution are placed between the two bauerite sheets, form sandwich sandwich structure, so just between two BOPP films, formed one deck 2-10 μ m liquid film; Place illumination 40-120 second under the uviol lamp then; With two BOPP films separately, be immersed in the deionized water hydrolysis more than 15 minutes after the illumination, it is clean with deionized water and acetone rinsing to take out the back, 50 ℃ of oven dry down.
The present invention is by the modification to matrix, the optimization of capping technology, the whole hydrophilic modification of fluid channel has solved common problem in the present micro-fluid reactor manufacture process, realized a kind of illumination synthesis of nano particle, complete organic transparent micro-fluid reactor of particulates such as polymer microballoon.
The specific embodiment
Describe the present invention in detail below in conjunction with accompanying drawing.
1. the material construction of fluid channel
Fluid channel should be compatible mutually with multiple solvent and eroding chemical, as oxolane, toluene, acetone, acids (example hydrochloric acid) and bases (as NaOH).SU8 is that a kind of desirable fluid channel makes up material, (depth-to-width ratio can reach more than 10 because it is particularly suitable for making the high-aspect-ratio fluid channel, the degree of depth can reach more than 500 microns), and possess excellent chemical resistance and mechanical performance, and based on the workability of UV LIGA and X-ray LIGA.The vitrification point (Tg) of the SU8 membrane structure under the standard technology can reach 150 ℃, and Young's modulus is 2396-2605MPa under the room temperature, modulus of shearing 6.26 and 7.49MPa between.(as PMMA, PDMS) compare, SU8 has better resistivity to acetone, oxolane, hydrochloric acid and salpeter solution with other common polymer that are used to make fluid channel.
2.SU8 the modification of the selection of matrix and matrix in the fluid channel structure
Stainless steel, PMMA (polymethyl methacrylate), PEEK (polyether-ether-ketone) and silicon chip all can be used as the matrix material of SU8 fluid channel structure, the three has favorable mechanical performance and processing characteristics, but we still need to consider to weigh other major criterions of matrix, comprise: heat endurance, relatively the thermal coefficient of expansion of SU8 and with the compatibility of all kinds of solvents and chemicals.SU8, stainless steel, PMMA, PEEK, the typical heat coefficient of expansion (α) of oxolane (THF) and acetone, solubility parameters (δ) and Tg list in table 1.According to the data in the table 1, stainless steel and organic solvent have favorable compatibility and the favorable mechanical performance are arranged, but the difference on the thermal coefficient of expansion makes itself and SU8 incompatible; Can obviously find out PEEK in solvent resistance, all very excellent on heat endurance and the mechanical performance, and its solubility parameters and thermal coefficient of expansion and SU8 are very approaching, and compatibility is good, but the PEEK cost is high and opaque, is not suitable for photochemical reaction; PMMA and SU8 have good compatibility, and light transmission is good, and heat distortion temperature can reach about 100 ℃, and cost is low, and unique deficiency is the poor solvent resistance of PMMA, is vulnerable to very much the erosion of THF and acetone.
Table 1
SU8 stainless steel PMMA PEEK THF acetone
δ，(MPa)
1/2 23.0 19.0 21.3 18.6 19.3
σ，×10
-5/K -5.7 5600 5.0 5.8
Tg，℃ 150-240 105-115 172-178
In order to improve the anti-chemical reagent of PMMA, we utilize EA51 (a kind of epoxy acrylic quasi-oligomer, proud son of heaven Chemical Manufacture) by the surface light chemical reaction modification to be carried out on the PMMA surface.Then can be at EA51 surface spin coating SU8 glue, the sectional drawing that solidifies the back sample is shown in Figure 1B, because EA51 is the epoxy acrylic quasi-oligomer, SU8 is an epoxylite, the two compatibility is fine.Like this, the surface modification of matrix PMMA can improve the chemical resistance of matrix, simultaneously the adhesion between enhancing and SU8 microchannel.
3. the preparation of micro-fluid reactor
The structure of micro-fluid reactor runner adopts photoengraving technology, and process flow diagram is seen Fig. 1.
Process screwed hole 2 (only showing among the figure) in the import and export position (bottom) of PMMA matrix 1, for the ease of the spin coating glue-line, all are imported and exported 3 and are not all got through, shown in Figure 1A.
Utilize EA51 that PMMA matrix 1 is carried out surface modification, shown in Figure 1B.
Next solidify glue-line 4 surperficial spin coating SU8 2050 at EA51 and form glue-line 5, shown in Fig. 1 C.And carry out preceding baking, exposure and back and dry by the fire three step process.
Then, shown in Fig. 1 D, unexposed portion is developed, form fluid channel pattern 6.
Just can get through all import and export 7 (only showing among the figure) afterwards, shown in Fig. 1 E.
Next step promptly carries out capping to the fluid channel system of opening wide and handles: i.e. BOPP film 9 surperficial spin coating one deck EA51 glue-lines 8 of handling in hydroxylating, and shown in Fig. 1 F.
The capping glue-line is carried out pre-exposure, make the partial cross-linked curing of glue-line, be semisolid, not only kept adhibit quality but also be unlikely to block microchannel.Shown in Fig. 1 G, former unlimited fluid channel pattern is carried out capping, exposure is solidified glue-line fully to the top closure layer under tightly compacted state.So just, formed the microchannel 10 of sealing.
At last, the be locked PEEK screw 11 of conduit 12 of inside is screwed into screwed hole, makes conduit outlet 13 be fixed on the bottom of flow hole, with anti-leak., shown in Fig. 1 H.
4. the capping of micro-fluid reactor
In order to strengthen the light transmission of micro-fluid reactor, and save cost.In the capping step of fluid channel, the surperficial spin coating one deck EA51 glue-line of the Biaxially oriented polypropylene that we handled in hydroxylating (BOPP) film (uv transmittance is high, the about 40 μ m of thickness) (thickness 40 μ m-80 μ m).For the viscosity and the curing cross-linked degree of reconciling EA51; we add in EA51 and EA51 glue-line mass ratio is that 20-25wt% monomer diluent GMA (propylene oxide acid glycidyl ester) and 2-3wt% deep layer are solidified light trigger TPO (2; 4,6-trimethylbenzoyl diphenyl phosphate oxidation) and the cooperation light trigger 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) of 2-3wt%.Before capping, the capping glue-line is carried out the 10-30 pre-exposure (2mw/cm of second
2365nm).Shown in Fig. 1 E-1G, when the EA51 glue-line is the moving state of semi-fluid and has caking property, the unlimited fluid channel system that forms is before carried out capping.Under tightly compacted state, exposure is continued at the top afterwards, the capping glue-line is further solidified, keep-up pressure half an hour after the exposure.
Fig. 2 A-2B is a microphotograph, show typical fluid channel structure before capping after (Fig. 2 A) and the capping (Fig. 2 B) though small edge appears in the top infiltrates, but still can guarantee to keep unimpeded, and not stop up, this point can further be proved by fluid channel section S EM photo (Fig. 2 C, Fig. 2 D).Triple channel in fluid in polymer microballoon microreactor focusing partial structurtes and the nano particle microreactor partial structurtes that cross, be the meticulousst structure of size in the reactor, the most tiny place reaches 50 μ m, and the strike-through obstruction does not take place (Fig. 2 E, Fig. 2 F) yet after the capping.
As previously mentioned, EA51 and SU8 have similar epoxy construction unit, solidify the stronger adhesion of existence between the latter two.Can find out that the adhesion integral body between capping layer and SU8 fluid channel is very firm the photo (Fig. 3 A, 3B) before and after the capping from micro-fluid reactor, only that capping is good BOPP rete is torn and it can not be opened informal voucher (seeing the tear place among Fig. 3 B).
Experiment shows that ultraviolet light (particularly more than the wave band 300nm) transmitance of EA51 curing glue-line all is higher than the SU8 glue-line of same thickness (100 μ m).The transmitance data are referring to table 2.
Table 2 (luminous intensity unit: 100 μ w/cm
2Test wavelength: 365nm)
Original light intensity 39.6 52.8 88.2 111.4
Transmitance EA51 capping glue-line 76% 77% 79% 79%
SU8 capping glue-line 50% 48% 51% 51%
Hydroxylating for the BOPP film is handled extremely important, it is uniform spreading better that hydroxylated BOPP film can make EA51 solidify colloid, and the bonding reaction between hydroxyl and epoxide group can further strengthen the adhesion between BOPP and EA51 curing glue-line, and this patent all adopts the BOPP film of surface hydroxylation as the capping matrix.
5. the surface modification of base material and protection
At the thick EA51 glue-line of the matrix PMMA of cleaning surface spin coating one deck about 30-100 μ m; for the photocuring speed that improves EA51 and guarantee that glue-line solidifies evenly on different depth; adding and EA51 glue-line mass ratio are the deep layer light trigger TPO (2 of 5%-10% among the EA51; 4,6-trimethylbenzoyl diphenyl phosphate oxidation) and 1137 (2-hydroxy-2-methyls-1-phenyl-1-acetone).Leave standstill made EA51 glue-line nature levelling in 5 minutes after, place (the light intensity 7-8mW/cm of 254nm place that exposes high pressure (1000W) uviol lamp under
2) 1-2 minute, make EA51 curable adhesive layer film forming, finish surface modification.Shown in Fig. 4 A, can the firm EA51 of coated one deck on the PMMA matrix, when breaking disconnected sample off with the fingers and thumb obvious break-off can not take place.After the matrix PMMA modification, we can prepare the fluid channel pattern according to the SU8 standard photolithography process.In this experiment,,, form SU8 and solidify glue-line through preceding baking, exposure fully, back baking at the thick SU8 glue of the modified matrix surface about 40 μ m of spin coating one deck.EA51 can be with SU8 layer and PMMA layer good bond (PMMA, EA51 and SU8 three parts break-off can not take place), and protected PMMA directly not contact with reaction medium.The sectional drawing of sample is shown in Fig. 4 B.
Capping with the surface modification of polymer matrix film (the hydroxylating modification of BOPP film, Fig. 5)
The used polymer matrix film of capping glue-line is BOPP film (the about 40 μ m of thickness), and as previously mentioned, the hydrophilic modification of BOPP film is most important in its surperficial uniform spreading to capping glue.The process of BOPP film hydrophilicity-imparting treatment is as follows: the ammonium persulfate aqueous solution of configuration 15%-30%wt, drip an amount of solution between the BOPP of two cleanings film, two BOPP films that accompany ammonium persulfate solution are placed between the two bauerite sheets, form " sandwich is sandwich " structure, so just between two BOPP films, formed thin (the 2-10 μ m) liquid film of one deck.Whole system is placed (the light intensity 8-9mw/cm of 254nm place under the high pressure uviol lamp
2) illumination 40-120 second.With two BOPP films separately, be immersed in the deionized water hydrolysis 15 minutes to 12 hours after the illumination, it is clean with deionized water and acetone rinsing to take out the back, 50 ℃ of oven dry 5 minutes down.In the said hydrolyzed step, hydrolysis can obtain the BOPP film of surperficial sulfate radicalization in 15 minutes, hydrolysis can obtain the BOPP film of surface hydroxylation more than 12 hours, the both can make EA51 solidify colloid and tie up to BOPP film surface uniform spreading and become thin adhesive layer, and solidifies the back at thin adhesive layer and keep good bonding force.
7. the hydrophilic modification of fluid channel
For micro-fluid reactor is more suitable in aqueous phase reactions, particularly for the polymer microballoon micro-fluid reactor,, can locate to take place to change mutually at " fluid focusing mouth " if fluid channel is hydrophilic inadequately, can not form the oil-in-water structure effectively.To this, we have adopted several method that fluid channel is carried out hydrophilic modification, and the modification result is characterized by the contact angle tester and is listed in table 3.
Table 3
Comprehensive above data as can be seen, the hydroxylating processing can both be played reasonable hydrophiling effect for SU8 and EA51 system, and hydroxylating is more obvious for the effect of EA51 system.Fig. 6 A and 6B are the contact angle test photo through the SU8 of hydroxylating modification and EA51 surface, as can be seen, after the hydroxylating modification, the hydrophily of the structure material of fluid channel is largely increased, water droplet can further be sprawled (Fig. 6 B) on the EA51 surface, after the EA51 hydroxylating than more hydrophilic after the SU8 hydroxylating.
8. the structure of fluid channel pattern (figure sees Fig. 1)
The processing dimension of the base of PMMA shown in Figure 1A 1 is 65mm * 65mm * 10mm, process the 6-32 screwed hole 2 (in figure only show) of the degree of depth between 5-7mm in import and export positions (bottom), import and export 3 (for the ease of gluing, all import and export are not all got through) the aperture be 1mm, the about 1mm of the degree of depth.At first, PMMA matrix 1 is carried out surface modification, form one deck EA51 protective layer in the surface, shown in Figure 1B according to method described in the example 1.
Under 25 ℃ of the room temperatures, will be fixed on through the matrix PMMA of surface modification on the pallet of spin coating instrument, the SU-8-2050 (MicroChem production) that the surface drips about 1ml avoids producing bubble as far as possible during dropping.(1) spin coating: regulate rotating speed, make SU-8 glue carry out slow-speed of revolution spin coating (rotating speed is increased to 1000 rev/mins gradually by 500 rev/mins) in 15 seconds, spin coating is 30 to 40 seconds under the high afterwards rotating speed (about 1000 rev/mins).SU-8 glue-line 5 thickness that obtain under this condition are about 150 μ m.In order to obtain thicker glue-line, can after preceding baking, cooling, continue spin coating SU-8 glue-line according to the method described above.After the spin coating static 10 minutes so that SU8 glue-line nature levelling; (2) preceding baking: in a conventional oven, 65 ℃ following 20 minutes, rise to 95 ℃ with 1 ℃/minute speed afterwards, for the thick glue of 150 μ m, 95 ℃ kept 80 minutes down.Make glue-line slowly reduce to room temperature after the preceding baking; (3) exposure: make SU-8 glue-line surface closely cover the photomask with fluid channel pattern, the standard exposure amount of the SU-8 glue-line that 150 μ m are thick is 300mJ/cm
2For SU-8 glue and photomask are fitted tightly, focus on non-parallel light simultaneously, can between glue-line and photomask, drip glycerine, tightly compacted, form the glycerine liquid film; After the exposure glycerine of remnants is cleaned with deionized water, and deionized water is blotted; (4) back baking: in a conventional oven, 65 ℃ kept 5 minutes down, rose to 95 ℃ with 5 ℃/minute speed then, and for the thick glue of 150 μ m, 95 ℃ kept 5 minutes down.Slowly cool to room temperature; (5) develop: the SU-8 that will the back baking finishes puts into the special-purpose developer solution of SU-8 and develops, and notes the exposure area is immersed in the developer solution fully.Container is put into constant temperature oscillator, be adjusted to 150 rev/mins, 40 ℃ vibrated 8～10 minutes down, and making has sufficient relative motion between developer solution and the SU-8.Form fluid channel pattern 6.Further sonic oscillation is cleaned remaining sizing material in the runner afterwards.
9. the preparation of small runner and hydroxylating BOPP film are to the sealing effectiveness of small size fluid channel
After according to above-mentioned steps micro-fluid reactor being carried out capping, fluid channel is carried out the SEM profile scanning, with the fluid channel structure that shows that further sealing is complete.Shown in Fig. 7 A-7B, fluid channel is wide to be the 40-200 micron, reaches 200 microns deeply.The phenomenon that sizing material stops up runner does not take place after the capping.This is because the EA51 of the moving state of semi-fluid has higher surface tension, is enough to prevent the sizing material seepage.And toughness that semi-solid EA51 possessed and surface tension make it form one deck homogeneous between fluid channel patterning and BOPP film, contact film completely.EA51 capping glue-line after solidifying fully can be realized the tight capping to fluid channel.Shown in Fig. 7 A, steep not enough less than the flow path wall of 50 microns fluid channel, mainly be because non-parallel light source is bigger than influence to the live width of small size fluid channel.There is small crack in fluid channel bottom with matrix, mainly is because the section cutting meeting during sample preparation causes certain destruction to sample.
The microreactor of example 1 preparation polymer microballoon
Fig. 8 is the micro-fluid reactor of preparation polymer microballoon particulates such as (surface-functionalized) nucleocapsid structures.The preparation technology of reactor as previously mentioned.In order to slow down the increase amplitude of pressure, be convenient to direct the flow of liquid either into and flow out the microchannel, the import and export passage place of micro-fluid reactor all adopts the width gradual change design.
As shown in Figure 8, the polymer microballoon microreactor has three intake channels 14,15 and an exit passageway 16, and terminal separately has import (outlet) hole 17 (only marking among the figure) of a diameter 1mm.Decentralized photo (as oiliness monomer phase) is flowed into by the intake channel 14 of centre, and continuous phase (as water) is flowed into by the intake channel 15 of both sides.Three strands of microfluids are by " microfluid focusing mouth " 18 o'clock (enlarged drawing is referring to Fig. 2 F), and the fluid channel size is dwindled suddenly, and under the effect of shearing force, the microfluid liquidus ruptures, and generates micro-capsule bubble (as the monomer droplet of oil-in-water type).Then initiated polymerization, cross-linking reaction under the ultraviolet lighting condition, monomer droplet is converted into polymer microballoon in the reaction channel 19 that wriggles.Intake channel 14,15 length are 19-22mm, wide 250-550 μ m, " microfluid focusing mouth " 18 long 100 μ m, wide 50-150 μ m, reaction channel 19 long 215mm, wide 550 μ m.The fluid channel depth bounds is at 150-600 μ m, and depth-to-width ratio reaches as high as 4.
The microreactor of example 2 preparation nano particles
Fig. 9 for be used to prepare nano particle (as Au, Ag, micro-fluid reactor Co).The preparation technology of reactor as previously mentioned.Increase amplitude in order to slow down pressure, be convenient to direct the flow of liquid either into and flow out the microchannel, the import and export passage place of micro-fluid reactor all adopts the width gradual change design.
As shown in Figure 9, the nano particle microreactor has three intake channels 20,21 and an exit passageway 22, and wherein 20 is first intake channel, 21 is second intake channel, and the terminal of all import and export passages all has import (outlet) hole 23 (only marking among the figure) of a diameter 1mm.We can add new reactant in second import 21, it is mixed with the micro fluid reaction liquid of front react.Two passages of first import 20 can add different reactants respectively, for the ease of mixing, the narrowest 25 wide 30-70 μ m (enlarged drawing is referring to Fig. 2 E) of place of fluid channel, W-response passage 24 wide 150 μ m-225 μ m, long 630mm, the fluid channel depth bounds is at 100-350 μ m, and depth-to-width ratio reaches as high as 5.
Description of drawings
Fig. 1 is that the structure of micro-fluid reactor runner adopts the photoengraving process flow diagram.
Fig. 2 is the microphotograph of fluid channel structure before and after capping.
Fig. 3 is the photo of fluid channel reactor before and after capping.
Fig. 4 A is coated one deck EA51 figure on the PMMA matrix among Fig. 4; Fig. 4 B is the sectional drawing of sample.
Fig. 5 is the hydroxylating modification figure of BOPP film.
Fig. 6 A and 6B are respectively through the SU8 of hydroxylating modification and the contact angle test photo on EA51 surface among Fig. 6.
Fig. 7 carries out after the capping fluid channel being carried out SEM profile scanning figure for micro-fluid reactor.
Fig. 8 is the micro-fluid reactor of preparation polymer microballoon particulates such as (surface-functionalized) nucleocapsid structures.
Fig. 9 for be used to prepare nano particle (as Au, Ag, micro-fluid reactor Co).
Claims (3)
1. one kind is suitable for photochemically reactive polymer based microfluid reactor, it is characterized in that, comprises successively from bottom to up:
Importing and exporting the matrix that the position has the PMMA of screwed hole, be screwed into the be locked PEEK screw of conduit of inside in this screwed hole, this conduit outlet is fixed on the bottom of import and export;
The EA51 glue-line of PMMA matrix surface spin coating;
At the SU8 glue-line of EA51 glue-line surface spin coating, this SU8 glue-line unexposed portion develops and forms the fluid channel pattern;
The capping glue-line that BOPP film surface spin coating one deck EA51 glue-line of handling in hydroxylating forms, this capping glue-line carries out capping to the SU8 glue-line fluid channel pattern that opens wide.
2. according to the preparation method of the described reactor of claim 1, it is characterized in that, may further comprise the steps:
A: process the screwed hole that the top that is connected with external equipment is not got through in the import and export position of PMMA matrix;
B:, carry out surface modification at the matrix PMMA of cleaning surface spin coating one deck EA51 glue-line;
C:, and carry out preceding baking, exposure and back baking three step process at EA51 glue-line surface spin coating SU8 glue-line;
D: then SU8 glue-line unexposed portion is developed, form the fluid channel pattern;
E: get through all import and export;
F: BOPP film surface spin coating one deck EA51 glue-line of handling in hydroxylating forms the capping glue-line; And the capping glue-line carried out pre-exposure, and make the partial cross-linked curing of glue-line, be semisolid;
G: the fluid channel pattern that opens wide is carried out capping, and exposure is solidified glue-line fully to the top closure layer under tightly compacted state, has just formed the microchannel of sealing;
H: the be locked PEEK screw of conduit of inside is screwed into screwed hole, makes conduit outlet be fixed on the bottom of import and export.
3. preparation method according to claim 2 is characterized in that, the hydroxylating treatments B OPP membrane process in the described step F is:
The ammonium persulfate aqueous solution of configuration 15%-30%wt, drip this ammonium persulfate aqueous solution between the BOPP of two cleanings film, two BOPP films that accompany ammonium persulfate solution are placed between the two bauerite sheets, form sandwich sandwich structure, so just between two BOPP films, formed one deck 2-10 μ m liquid film; Place the light intensity 7-8mW/cm of 254nm place then
2Uviol lamp under illumination 40-120 second; With two BOPP films separately, be immersed in the deionized water hydrolysis more than 15 minutes after the illumination, it is clean with deionized water and acetone rinsing to take out the back, 50 ℃ of oven dry down.
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| CN101549275B (en) * | 2009-04-10 | 2011-05-11 | 南京工业大学 | Integrated microfluid reactor |
| CN101571536B (en) * | 2009-06-09 | 2012-12-05 | 宋玉军 | Preparation process of single nanoparticle and array-based biological molecule detector thereof |
| CN105895805B (en) * | 2016-05-09 | 2018-08-24 | 浙江海洋大学 | A kind of active layer preparation method suitable for polymer solar battery |
| CN110773089A (en) * | 2019-11-05 | 2020-02-11 | 山东奇谱创能生物科技有限公司 | Multi-channel chemical micro-reaction equipment based on single light beam |
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| US20060014271A1 (en) * | 2004-07-16 | 2006-01-19 | Yujun Song | Fabrication of a completely polymeric microfluidic reactor for chemical synthesis |
| CN101008594A (en) * | 2007-01-25 | 2007-08-01 | 重庆大学 | Micro-fluidic chip containing sample pre-treatment film and production method therefor |
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