WO2005123241A1 - Appareil et procede permettant d'effectuer des reactions photochimiques - Google Patents

Appareil et procede permettant d'effectuer des reactions photochimiques Download PDF

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Publication number
WO2005123241A1
WO2005123241A1 PCT/GB2005/002436 GB2005002436W WO2005123241A1 WO 2005123241 A1 WO2005123241 A1 WO 2005123241A1 GB 2005002436 W GB2005002436 W GB 2005002436W WO 2005123241 A1 WO2005123241 A1 WO 2005123241A1
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WO
WIPO (PCT)
Prior art keywords
irradiation zone
conduit
inlet
fluid
outlet
Prior art date
Application number
PCT/GB2005/002436
Other languages
English (en)
Inventor
Robert Huw Davis
Daniel David Palmer
Original Assignee
Q Chip Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0413839A external-priority patent/GB0413839D0/en
Priority claimed from GB0502398A external-priority patent/GB0502398D0/en
Application filed by Q Chip Limited filed Critical Q Chip Limited
Publication of WO2005123241A1 publication Critical patent/WO2005123241A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00833—Plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/00862—Dimensions of the reaction cavity itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00925—Irradiation
    • B01J2219/00934—Electromagnetic waves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00925—Irradiation
    • B01J2219/00934—Electromagnetic waves
    • B01J2219/00936—UV-radiations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip

Definitions

  • the present invention relates to a method and apparatus for performing photochemical reactions, including an apparatus and method producing a segmented flow of liquid.
  • Photochemistry is an extremely powerful tool for the synthetic chemist, providing a route to synthetically demanding chemical functionalities and moieties.
  • lab-scale photochemical reactions have some disadvantages, for example, long reaction times, and attenuation of incident light by large (often stationary) solvent volumes.
  • an apparatus for the performance of photochemical reactions comprising (i) a microfluidic device comprising a first inlet for the introduction of a first fluid, the first inlet being in fluid communication with an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit extending in an indirect manner from the irradiation zone inlet to the irradiation zone outlet, (ii) a source of electromagnetic radiation operable to illuminate the irradiation zone with electromagnetic radiation.
  • Such an apparatus is effective in performing photochemical reactions, the photochemical reaction primarily being carried out in the irradiation zone when reaction components are exposed to the electromagnetic radiation from the source of electromagnetic radiation.
  • the term "indirect” refers to the irradiation zone conduit taking a path that is not a straight line or shortest path between the irradiation zone inlet and the irradiation zone outlet .
  • microfluidic is well-understood by those skilled in the art and in particular includes those devices having conduits having diameters of about 1mm or less.
  • the conduits preferably have a diameter of from 0.05 to 0.5mm and more preferably of from 0.05 to 0.1mm.
  • the irradiation zone outlet is preferably in communication with a device outlet for the egress of reaction products.
  • the irradiation zone conduit comprises one or more curved portions or bends in the flow path between the irradiation zone inlet and the irradiation zone outlet .
  • an apparatus for the performance of photochemical reactions comprising (i) a icrofluidic device comprising a first inlet for the introduction of a first fluid, the first inlet being in fluid communication with an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit comprises one or more bends or curved portions in the flow path between the irradiation zone inlet and the irradiation zone outlet, (ii) a source of electromagnetic radiation operable to illuminate the irradiation zone with electromagnetic radiation .
  • the irradiation zone conduit forms an S or Z shape in the flow path between the irradiation zone inlet and the irradiation zone outlet.
  • the irradiation zone conduit may comprise a serpentine, spiral or tortuous formation in the flow path between the irradiation zone inlet and the irradiation zone outlet.
  • the irradiation zone conduit may comprise a switchback formation in the flow path between the irradiation zone inlet and the irradiation zone outlet.
  • the length of the irradiation zone conduit between the irradiation zone inlet and the irradiation zone outlet is from 2A to 20A units, more preferably from 5A to 20A units and further more preferably from 8A to 15A units.
  • the length of the irradiation zone conduit between the irradiation zone inlet and the irradiation zone outlet may, for example, be fr-o 5cm to 40cm, when the irradiation zone has a maximum diameter of from 0.5 to 4cm.
  • the device is provided with a means for inhibiting transmission of electromagnetic radiation between the irradiation zone and the first inlet.
  • the means for inhibiting transmission of electromagnetic radiation may comprise one or more bend or bends in a conduit (typically upstream of the irradiation zone and downstream of the first inlet), a switchback arrangement in a conduit (typically upstream of the irradiation zone and downstream of the first inlet) , an internal surface of a conduit being coating with non-reflective material or a discontinuity in a conduit, such as a drop or fall from one level to another.
  • the apparatus is preferably provided with a means for urging reagents from the first inlet to the irradiation zone outlet, such as a pump.
  • the fluid path between the first inlet and the irradiation zone outlet may be formed by one or more conduits.
  • the device may be provided with a second inlet for the introduction of a second fluid.
  • the first inlet is preferably associated with a first conduit and the second inlet is preferably associated with a second conduit. It is preferred that the first and second conduits merge to form a third conduit, which is preferably upstream of the irradiation zone.
  • the third conduit would typically be in communication with the irradiation zone conduit so that fluid could be moved from the third conduit to the irradiation zone.
  • the third conduit and the irradiation zone conduit may not be distinguishable from one another as separate conduits, for example, in the case where the third conduit and irradiation zone conduit have the same diameter or internal size .
  • the first fluid is immiscible with the second fluid, and that the first conduit and the second conduit merge to form a third conduit (or the third conduit is formed with a constriction or other discontinuity) such that fluid in the first and second conduits form into a flow of alternate segments in the third conduit.
  • the third conduit would typically be in communication with the irradiation zone conduit so that the flow of alternate segments could be moved to the irradiation zone conduit for exposure to electromagnetic radiation .
  • the device may further be provided with a third inlet for the introduction of a third fluid.
  • the third inlet is preferably associated with a fourth conduit. It is preferred that the fourth conduit merges with one or more of the first, second and third conduits, preferably upstream of the irradiation ' zone. It is preferred that the fourth conduit merges with the third conduit to form a fifth conduit.
  • the first, second, third and fourth conduits would typically be arranged so that fluids may be transferred from those conduits (possibly via other conduits, such as ' the fifth conduit) to the irradiation zone conduit.
  • the third fluid may be immiscible with the first and second fluids, and the third conduit may merge with the fourth conduit to form a fifth conduit (or the fifth conduit is provided with a constriction or other discontinuity) , such that fluid in the third and fourth conduits form into a flow of alternate segments in the fifth conduit.
  • the fifth conduit would typically be in communication with the irradiation zone conduit so that the flow of alternate segments could be moved to the irradiation zone conduit for exposure to electromagnetic radiation.
  • the fifth conduit and the irradiation zone conduit may not be distinguishable from one another as separate conduits, for example, in the case where the fifth conduit and irradiation zone conduit have the same diameter or internal size.
  • a conduit upstream of the irradiation zone, a conduit is provided with an enlargement in cross-section. Such an enlargement in cross-section may allow segments in a segmented flow to form a more spherical shape prior to irradiation.
  • the surfaces of the conduits mentioned above that come into contact with the fluids used in the device may be provided with low energy materials. This may be achieved by forming channels or conduits into a substrate of low energy material or by forming channels or conduits into a substrate of relatively high energy material and coating the channels or conduits so formed with a low energy material .
  • partial channels or conduits may be formed in two substrates such that, when the substrates are mounted together, the partial channels of one substrate cooperate with the respective partial channels of the other substrate to form complete channels or conduits.
  • the microfluidic device may comprise two substrates having low energy surfaces (typically around that of fluoropolymers, below 22 mN/m, and preferably below 18 mN/m) , the two substrates preferably being placed co- facially one against the other.
  • One or more (preferably the irradiation zone conduit and more preferably all) of the conduits provided in the device may be formed in one of the substrates (this being known as the base substrate) . This may typically be achieved by milling the conduit or conduits using conventional milling technology, or by using laser ablation for example.
  • the low energy surfaces may be provided by fluoropolymer based substrate layers, which may be composed of bulk fluoropolymer, or fluoropolymer or fluoropolymer-based coatings applied to other non-fluoropolymer bulk material substrate layers.
  • One of the substrates (preferably the substrate not being the base substrate) may be at least partially transparent to the said electromagnetic radiation.
  • the source of electromagnetic radiation is a source of ultra-violet radiation.
  • two or more " devices may be present together. This is particularly advantageous when it is desirable to produce a segmented flow in a confined or restricted space. It is preferable that a plurality of devices is present, for example more than five.
  • a third aspect of the present invention provides an apparatus for the performance of photochemical reactions, the apparatus comprising (i) a microfluidic device comprising a plurality of first inlets for the introduction of a first fluid, and a plurality of irradiation zone conduit, each first inlet being in fluid communication with an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, wherein one, and preferably each, of the irradiation zone conduits extend in an indirect manner from the respective irradiation zone inlet to the respective irradiation zone outlet, (ii) a source of electromagnetic radiation operable to illuminate each irradiation zone with electromagnetic radiation.
  • One or more of the irradiation zone conduits may be provided with one or more bends or curved portions in the flow path between the respective irradiation zone inlet and the respective irradiation zone outlet.
  • a fourth aspect of the present invention provides an apparatus for the performance of photochemical reactions, the apparatus comprising (i) a microfluidic device comprising a plurality of first inlets for the introduction of a first fluid, and a plurality of irradiation zone conduit, each first inlet being in fluid communication with an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, wherein one, and preferably each, of the irradiation zone conduits comprises one or more bends or curved portions in the flow path between the irradiation zone inlet and the irradiation zone outlet (ii) a source of electromagnetic radiation operable to illuminate each irradiation zone with electromagnetic radiation.
  • each irradiation zone outlet is in communication with a device outlet for the egress of reaction products.
  • the device of the apparatus of the third and fourth aspects of the present invention may incorporate those features described above with respect to the apparatus and device of the first and second aspects of the present invention.
  • each irradiation zone conduit may comprise a spiral formation.
  • One or more of the irradiation zone outlets may be arranged to be in communication with a common device outlet. It is preferred that such a device outlet is provided by an aperture and that a plurality of, and preferably all, of the irradiation zone outlets are located at said aperture.
  • the irradiation zone has an area of A 2 (units) 2
  • the sum of lengths of each of the irradiation zone conduits between the respective irradiation zone inlets and the respective irradiation zone outlets is from 2A to 20A units, more preferably from 5A to 20A units and further ' more preferably from 8A to 15A units.
  • a microfluidic device suitable for use in the apparatus of the first, second, third and fourth aspects of the present invention.
  • a method for performing a photochemical reaction comprising (i) providing a microfluidic device comprising an • irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit extending in an indirect manner from the irradiation zone inlet to the irradiation zone outlet, (ii) providing a reagent or reagents for a photochemical reaction (iii) causing the reagent or reagents to flow from the irradiation zone inlet to the irradiation zone outlet (iv) irradiating the reagent or reagents as they pass from the irradiation zone inlet to the irradiation zone outlet so as to promote the photochemical reaction .
  • a method for performing a photochemical reaction comprising (i) providing a microfluidic device comprising an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, wherein the irradiation zone conduit comprises one or more bends or curved portions in the flow path between the irradiation zone inlet and the irradiation zone outlet, (ii) providing a reagent or reagents for a photochemical reaction (iii) causing the reagent or reagents to flow from the irradiation zone inlet to the irradiation zone outlet (iv) irradiating the reagent or reagents as they pass from the irradiation zone inlet to the irradiation zone outlet so as to promote the photochemical reaction.
  • the time taken for the reagent or reagents to pass from the irradiation zone inlet to the irradiation zone outlet is from 10 seconds to 2 minutes, for example, when the path length from the irradiation zone inlet to the irradiation zone outlet is from 5cm to 40cm, more preferably when said path length is from 10cm to 20cm.
  • the reagents may be mixed prior to the introduction of the reagents into the device.
  • a first reagent may be introduced via a first conduit, and a second reagent (being miscible with the first reagent) may be introduced via a second conduit, the first and second conduits merging at a third conduit.
  • first and second reagents are immiscible then it is preferred that the first conduit and the second conduit merge to form a third conduit such that fluids in the first and second conduits form into a flow of alternate segments in the third conduit.
  • the third conduit may be formed with a constriction or other discontinuity such that fluids in the first and second conduits form into a flow of alternate segments in the third conduit.
  • the method may further comprise introducing a third reagent via a fourth conduit, wherein the third fluid may be immiscible with the first and second fluids, and the third conduit may merge ' with the fourth conduit such that fluid in the third and fourth conduits form into a flow of alternate segments in the fourth conduit.
  • the fourth conduit may be provided with a constriction or other discontinuity such that fluids in the third and fourth conduits form into a flow of alternate segments in the fourth conduit.
  • An eighth aspect df the present invention provides a method for performing a photochemical reaction, the method comprising: (i) providing a microfluidic device comprising an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit extending in an indirect manner from the irradiation zone inlet to the irradiation zone outlet, (ii) providing two or more miscible reagents for a photochemical reaction (iii) mixing the two or more miscible reagents to form a mixture (iv) causing the mixture to flow from the irradiation zone inlet to the irradiation zone outlet (v) irradiating the mixture as it passes from the ⁇ irradiation zone inlet. to the irradiation zone outlet so as to promote the photochemical reaction.
  • a ninth aspect of the present invention provides a method for performing a photochemical reaction, the method comprising: (i) providing a microfluidic device comprising an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit comprising one or more bends or curved portions in the flow path between the irradiation zone inlet and the irradiation zone outlet, (ii) providing two or more miscible reagents for a photochemical reaction (iii) mixing the two or more miscible reagents to form a mixture (iv) causing the mixture to flow from the irradiation zone inlet to the irradiation zone outlet (v) irradiating the mixture as it passes from the irradiation zone inlet to the irradiation zone outlet so as to promote the photochemical reaction.
  • the mixture is preferably irradiated with ultraviolet radiation.
  • a tenth aspect of the present invention provides a method for making polymeric particulates, the method comprising: (i) providing a microfluidic device comprising an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit extending in an indirect manner from the irradiation zone inlet to the irradiation zone outlet (ii) providing a polymeric precursor and an initiator that, on exposure to electromagnetic radiation, initiates the polymerisation of the precursor (iii) providing a carrier fluid that is immiscible with the polymeric.
  • An eleventh aspect of the present invention provides a method for making polymeric particulates, the method comprising: (i) providing a microfluidic device comprising an irradiation zone conduit having an irradiation zone inlet where a fluid enters the irradiation zone and an irradiation zone outlet where a fluid leaves the irradiation zone, the irradiation zone conduit comprising one or more bends or curved regions in the flow path between the irradiation zone inlet and the irradiation zone outlet, (ii) providing a polymeric precursor and an initiator that, on exposure to electromagnetic radiation, initiates the polymerisation of the precursor (iii) providing a carrier fluid that is immiscible with the polymeric precursor and the initiator (iv) mixing the polymeric precursor and the initiator to form a mixture (v) causing the mixture and the carrier fluid to form a segmented flow (vi) causing the segmented flow to pass from the irradiation zone inlet to the i
  • the device is arranged for laminar flow throughout. This is usually achieved using low energy surfaces such as those discussed above to define the fluid flow paths through the device.
  • a device for producing a segmented flow of liquid which device includes: a first conduit arranged to receive a first fluid and a second conduit arranged to receive a second fluid, the first conduit and the second conduit merging to form a further flow conduit, in which, in use, the first fluid and the second fluid are permitted to flow, preferably to form a laminar flow, the further flow conduit merging with a carrier fluid conduit to form a segmented flow conduit, the segmented flow conduit being formed with a constriction or other discontinuity such that, in use, fluid in the further flow conduit and the carrier fluid conduit form into a flow of alternate segments in the segmented flow conduit.
  • the carrier fluid conduit is preferably arranged to contain a carrier fluid which is typically immiscible with the first and second fluid.
  • a typical carrier fluid is an organic fluid.
  • the discontinuity includes a region of changed or alterable surface energy, or a further conduit which joins the segmented flow conduit.
  • the constriction may preferably include the internal configuration of the segmented flow conduit. It is therefore further preferred that the cross-sectional area of the segmented flow conduit is substantially less than the sum of the cross-sectional area of the further flow conduit and the carrier fluid conduit .
  • the segmented flow conduit is shaped or dimensioned to include one or more curve, bend or indentation.
  • the curve, bend or indentation assists in the mixing of the contents of each segment which, prior to reaching a bend, indentation or curve, may still have a substantially laminar structure.
  • the curve, indentation or bend is preferably downstream from the constriction or other discontinuity.
  • a portion of the segmented flow conduit is shaped and dimensioned to provide an irradiation zone.
  • the irradiation zone is arranged to maximise exposure to, for example, an external radiation source.
  • the irradiation zone is typically downstream from the constriction or other discontinuity, further preferably down stream from the curve or bend.
  • constriction or other discontinuity is preferably substantially at, or close to, the juncture where the further flow conduit merges with the carrier fluid conduit.
  • the irradiation zone may therefore be laid out in a spirallike shape or a z-shape.
  • segmental flow conduit has a length of between 5cm and 40cm when in the spiral-like shape or z-shape.
  • the irradiation zone can be any shape that has the desired effect of maximising exposure to an external source .
  • the segmented flow conduit may have an internal- reflection coating.
  • the internal- reflection coating enhances the "increased-exposure" effect .
  • the device may further include an external radiation source.
  • the external radiation source may be a light source which further preferably is arranged to be delivered via a light guide, which may be adapted to produce a collinated light beam.
  • the device is masked with a reflective shield (which may or may not be an integral part of the device) .
  • the reflective shield prohibits, or at least substantially reduces, the uncontrolled local absorption of radiation in the first conduit, the second conduit, the further flow conduit and/or the segmented flow conduit.
  • the device may be a unitary device, or alternatively may be manufactured from a plurality of separate conduits which are fused or joined together.
  • the device may include a third and optionally a fourth conduit arranged to merge with the first and second conduit to form the further flow conduit, or alternatively to merge with the further flow conduit.
  • the device may include more conduits arranged to merge with the further flow conduit.
  • Each conduit is preferably arranged to receive a fluid (further preferably a miscible fluid). It is self evident to a person skilled in the art, that the number of fluid conduits feeding to the further flow conduit is dependent on the number of fluids that it is desired to combine in each segment .
  • the device offers a number of advantages over conventional devices for photochemical reactions, one such advantage includes decreased reaction times. This is due to the high surface/volume ratio of the fluid circuit in the device. In addition, as only small (typically nano or pico litre) volumes are exposed to a radiation source at any one time, there is significantly less attenuation of incident light by solvent, making the reaction more efficient per photon. Furthermore, efficient mixing can be achieved without the need for external agitation, producing homogenised reaction mixtures, which can be exposed to a tuned radiation source for a controlled time.
  • two or more devices may be present together. This is particularly advantageous when it is desirable to produce a segmented flow in a confined or restricted space. It is preferable that a plurality of devices are present, for example more than five.
  • a device for producing two or more segmented flows of liquid including: two or more first conduits arranged to receive a first fluid and two or more second conduits each arranged to receive a second fluid, each first conduit merging with a respective second conduit to form a further flow conduit, each further flow conduit merging with a respective carrier fluid conduit to form a respective segmented flow conduit, each segmented flow conduit being formed with a constriction or other discontinuity such that fluid in each further flow conduit and each carrier fluid conduit form into a flow of alternate segments in each respective segmented flow conduit.
  • the device includes a plurality of first conduits, a plurality of second conduits merging to form respective further flow conduits, each further flow conduit being for merging with a respective carrier fluid conduit to form a respective segmented flow conduit, each segmented flow conduit being formed with a constriction or other discontinuity such that fluid in each further flow conduit and each carrier fluid conduit form into a flow of alternate segments.
  • the first conduits, the second conduits, the further flow conduits and segmented flow conduits are substantially as described hereinbefore with reference to the first aspect of the present invention.
  • fluid entering each first fluid conduit is the same fluid, however, it is envisaged that the device is arranged such that a different fluid enters each first conduit.
  • fluid entering each second fluid conduit is the same fluid, however, it is envisaged that the device is arranged such that a different fluid enters each first conduit.
  • segmented flow conduits are orientated such that they have a relatively small surface area in the plane of the device. It is particularly preferred that the segmented flow conduits are arranged in a spiral.
  • having the segmented flow conduits arranged in such an orientation permits the size of an irradiation zone (thereby the photochemical reaction takes place) to be substantially reduced.
  • a method for producing a segmented flow of a fluid which method includes: introducing a first liquid into a first inlet conduit and a second liquid into a second inlet conduit, the first conduit and the second conduit merging to form a further flow conduit; permitting the first liquid and the second liquid to achieve a laminar flow in the further flow conduit; merging the laminar flow with a carrier fluid in a segmented flow conduit, the segmented flow conduit including a constriction or discontinuity which causes the laminar flow and the carrier fluid to form a flow of alternate segments.
  • the method is preferably carried out in a device, substantially as described hereinbefore.
  • constriction or discontinuity is substantially in an area where the laminar flow and the carrier fluid meets.
  • first fluid and the second fluid are miscible liquids. Therefore, potentially reactive mixtures may be kept separate until such time that mixing is required.
  • the carrier fluid is further preferably a fluid which is immiscible.
  • the first fluid may include a dissolved photosensitivity compound (such as naphthalene, orthracene, POPOP) , whose purpose is to accelerate the photochemical reaction.
  • a dissolved photosensitivity compound such as naphthalene, orthracene, POPOP
  • the present invention may be utilised in a number of chemical reactions to which a micro-photochemical reactor might be applicable.
  • a non-exhaustive list may include:
  • the devices and methods of the present invention may preferably use fluids having liquid or liquid-like (as opposed to gaseous) properties.
  • Figure 1 represents a device according to the twelfth aspect of the present invention and a device as used in an apparatus according to the first and second aspects of the present invention
  • Figure 2 represents a device according to the thirteenth aspect of the present invention and a device as used in an apparatus according to the third and fourth aspects of the present invention, such a device having a plurality of irradiation zones.
  • the device is generally indicated by the numeral 1.
  • the first inlet conduit 2 (provided with first inlet 2a) merges with the second inlet conduit 3 (provided with second inlet 3a) at point 4 to form a further flow conduit 5.
  • a carrier fluid conduit 6 merges at point 7 with further flow conduit 5 to form a segmented flow conduit 8.
  • a discontinuity 9 (in the form of a constricted internal cross sectional area of the conduit) is substantially at the junction where conduits 5 and 6 merge.
  • Segmented flow conduit 8 bends at points 10, 11 and 12.
  • the segmented flow conduit 8 is formed into an irradiation zone conduit 14 in the form of a spiral in an irradiation zone 13.
  • the irradiation zone conduit 14 has a greater cross-sectional area than the segmented flow conduit 8, the enlargement in cross-section at point 16 allowing long, slug-like flow segments to form into a more spherical shape.
  • the irradiation zone conduit 14 has an irradiation zone inlet 17 where fluid enters the irradiation zone 13 and an irradiation zone outlet 15 where fluid leaves the irradiation zone 13.
  • the irradiation zone conduit extends in a spiral (and therefore in an indirect manner) from the irradiation zone inlet 17 to the irradiation zone outlet 15, "indirect" meaning that the irradiation zone conduit takes a path that is not a straight line or shortest path between the irradiation zone inlet and the irradiation zone outlet.
  • the first inlet conduit 2, second inlet conduit 3, further flow conduit 5, carrier flow conduit 6, segmented flow conduit 8 and irradiation zone conduit 14 are formed by machining the said conduits from a block of polytetrafluoroethylene (PTFE) polymer using a conventional milling machine.
  • the conduits typically have a square cross-section and typically have a channel width of between 50 to 300 microns. Smaller conduits may be produced using other techniques, such as laser ablation, photolithography and deep reactive ion etching.
  • a cover made from a low energy material in this case a 0.005 inch thick film of
  • PFA a perfluoroalkoxy copolymer, supplied by DuPont
  • PFA that is at least partially transparent to ultraviolet radiation
  • a non-UV transmissive blocking plate is arranged over the
  • PFA cover in order to prevent unwanted exposure of parts of the device other than irradiation zone to UV radiation.
  • a suitable aperture is provided in the blocking plate so that UV light can be transmitted to the irradiation zone.
  • a source of electromagnetic radiation is arranged in relation to the device 1 so that it illuminates the irradiation zone with the appropriate electromagnetic radiation.
  • This will typically be ultra-violet radiation (for example, that used to cure UV-sensitive polymers), but may be any type of electromagnetic radiation.
  • the materials forming the cover and blocking plate would be chosen appropriately, given the nature of the electromagnetic radiation used.
  • low energy materials other than PTFE may be used to form the block and materials other than PFA may be used to form the cover.
  • a coating of low energy material may be formed on a machined or otherwise channelled block of a relatively high energy material. Such a coating may be formed, for example, by plasma deposition, dipping, spin coating, lithography or Langmuir Blodgett deposition.
  • the device 100 comprises a plurality (in this case ten) of circuits (each labelled as 101) in which reactions can occur.
  • the device comprises a plurality of first inlet conduits 102 (only one of which is labelled for clarity) , each provided with a first inlet 102a, each first inlet conduit merging with a second inlet conduit 103 at point 104 to form a further flow conduit 105.
  • Each second inlet conduit is provided with a second inlet 103a.
  • a carrier fluid conduit 106 merges at point 107 with further flow conduit 105 to form a segmented flow conduit 108.
  • a discontinuity 109 (in the form of a constricted internal cross sectional area of the conduit) is substantially at the junction where conduits 105 and 106 merge.
  • Segmented flow conduit 108 bends at points 110, 111, 112, 113, 114, 115, 116. These bends increase mixing and help prevent transmission of electromagnetic radiation from irradiation zone 117 to any of the aforementioned conduits upstream of the irradiation zone.
  • Each segmented flow conduit 108 is formed into an irradiation zone conduit 119 in the form of a spiral in an irradiation zone 117.
  • the irradiation zone conduit 119 has a greater cross-sectional area than the segmented flow conduit 108, an enlargement in cross-section (not shown) upstream of the irradiation zone 117 allowing long, sluglike flow segments to form into a more spherical shape.
  • the irradiation zone conduit 119 has an irradiation zone inlet 120 where fluid enters the irradiation zone 117 and an irradiation zone outlet 121 where fluid leaves the irradiation zone 117.
  • the irradiation zone conduit extends in a spiral (and therefore in an indirect manner) from the irradiation zone inlet 120 to the irradiation zone outlet 121, "indirect" meaning that the irradiation zone conduit takes a path that is not a straight line or shortest path between the irradiation zone inlet and the irradiation zone outlet.
  • each irradiation zone conduit 119 forms a spiral thereby reducing the necessary overall surface area of the irradiation zone 117.
  • the contents of each irradiation zone conduit 119 exit via corresponding irradiation zone outlet 121.
  • All of the irradiation zone outlets are arranged around the periphery of a device outlet 118. In this manner, the fluids from each of the irradiation zone outlets may readily be collected together for removal from the device.
  • First inlet conduit 102, second inlet conduit 103, further flow conduit 105, carrier fluid conduit 106, segmented flow conduit 108 and irradiation zone conduit 119 are formed by machining the said conduits from a block of polytetrafluoroethylene (PTFE) polymer using a conventional milling machine.
  • a cover made from a low energy material in this case a 0.005 inch thick film of PFA (a perfluoroalkoxy copolymer, supplied by DuPont) that is at least partially transparent to ultraviolet radiation is provided on top of the PTFE block.
  • the diameter of the irradiation zone is about 68mm, with the length of each irradiation zone conduit being about 150mm.
  • a source of electromagnetic radiation is arranged in relation to the device 100 so that it illuminates the irradiation zone with the appropriate electromagnetic radiation.
  • the present invention will further be exemplified in the following example wherein the photochemical polymerisation of acrylamide / bisacrylamide mixtures was carried out.
  • a 40% aqueous mixture of acrylamide / bisacrylamide (ratio 19:1) was introduced into conduit 2.
  • a solution of the water soluble photo-initiator 2, 2-azobis (aminopropane) - dihydrochloride (approximately 200:1 by weight) was introduced into second inlet conduit 3. Laminar flow streams of these two fluids were established in further flow conduit 5.
  • An immiscible, organic fluid was introduced into carrier fluid conduit 6, and was allowed to contact the laminar flow in further flow conduit 5. As the immiscible organic fluid contacted the laminar fluid at discontinuity 9 a "slug-like" flow was produced.
  • Polyethylene glycol spheres with excellent uniformity of size were made as follows. A 20% aqueous mixture of polyethylene glycol dimethacrylate was introduced into first inlet conduit 2. A solution of water-soluble photo- initiator 2, 2-azobis (aminopropane) -dihydrochloride (approximately 200:1 by weight) was introduced into second inlet conduit 3. Laminar flow streams of these two fluids were established in further flow conduit 5. An immiscible, organic fluid was introduced into carrier fluid conduit 6, and was allowed to contact the laminar flow in further flow conduit 5.
  • the spheres had a diameter of 578 ⁇ 6 ⁇ m as measured using a calibrated microscope.
  • a 0.01M solution of benzophenone was dissolved in a 50:50 homogeneous mixture of 2-propanol and xylenes, and was degassed by bubbling oxygen-free nitrogen through the solution for 15 minutes.
  • the photo-reactive solution was then continuously pumped into the device 1 via first inlet conduit 2, second inlet conduit 3 and carrier fluid conduit 6 at a flow-rate of 15ml/h. One or two of these three conduits need not have been used.
  • reaction products were collected from the irradiation zone outlet 15 and subsequently analysed by G.C.M.S using a Thermoquest MD 800 with GC 8000 and AS 300, using a Varian column: 30m, 0.25 mm I.D., 0.25 ⁇ m FactorFour VF - 23ms at 70 kPa He.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un appareil permettant d'effectuer des réactions photochimiques et comprenant : (i) un dispositif microfluidique (1) présentant une première admission (2a) destinée à l'introduction d'un premier fluide, la première admission étant en communication fluidique avec un conduit de zone d'irradiation (14) possédant une admission de zone d'irradiation (17) où un fluide entre dans la zone d'irradiation et une évacuation de zone d'irradiation (15) où un fluide quitte la zone d'irradiation, le conduit de zone d'irradiation s'étendant d'une manière indirecte à partir de l'admission de la zone d'irradiation vers l'évacuation de la zone d'irradiation, (ii) une source de rayonnement électromagnétique conçue pour éclairer la zone d'irradiation au moyen de rayonnement électromagnétique.
PCT/GB2005/002436 2004-06-21 2005-06-21 Appareil et procede permettant d'effectuer des reactions photochimiques WO2005123241A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB0413839.2 2004-06-21
GB0413839A GB0413839D0 (en) 2004-06-21 2004-06-21 Device and method for producing segmented flow
GB0420003A GB0420003D0 (en) 2004-06-21 2004-09-08 Device and method for producing segmented flow
GB0420003.6 2004-09-08
GB0502398.1 2005-02-04
GB0502398A GB0502398D0 (en) 2005-02-04 2005-02-04 Device and method for producing spherical segmented flow

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WO2005123241A1 true WO2005123241A1 (fr) 2005-12-29

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WO2006082351A1 (fr) 2005-02-04 2006-08-10 Q Chip Limited Dispositif et procede pour produire un ecoulement segmente spherique
EP2184103A1 (fr) * 2008-11-11 2010-05-12 Onea Engineering Austria GmbH Réacteur modulaire
JP2010217162A (ja) * 2009-09-08 2010-09-30 Seiko Epson Corp 生体試料反応容器、生体試料充填装置、生体試料定量装置、及び生体試料反応方法
JP2010216984A (ja) * 2009-03-17 2010-09-30 Seiko Epson Corp 生体試料反応容器、生体試料充填装置、生体試料定量装置、及び生体試料反応方法
WO2013014466A1 (fr) 2011-07-28 2013-01-31 Q Chip Limited Dispositif et procédé de collecte de billes
CN102974255A (zh) * 2012-10-31 2013-03-20 中国科学院过程工程研究所 一种被动式螺旋微结构混合装置及应用
WO2012171983A3 (fr) * 2011-06-14 2013-05-10 Baxter International Inc. Procédé de production d'un produit polymérisé
CN105728071A (zh) * 2016-02-04 2016-07-06 中国地质大学（北京） 一种微流控芯片及其应用
CN106076218A (zh) * 2016-06-01 2016-11-09 苏州汶颢芯片科技有限公司 微流控芯片及碳量子点的合成方法
CN107597033A (zh) * 2017-09-29 2018-01-19 东莞理工学院 一种弹簧管式柔性微化学反应器

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US8114319B2 (en) 2005-02-04 2012-02-14 Q Chip Limited Device and method for producing spherical segmented flow
WO2006082351A1 (fr) 2005-02-04 2006-08-10 Q Chip Limited Dispositif et procede pour produire un ecoulement segmente spherique
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JP4706883B2 (ja) * 2009-03-17 2011-06-22 セイコーエプソン株式会社 生体試料定量方法
JP2010217162A (ja) * 2009-09-08 2010-09-30 Seiko Epson Corp 生体試料反応容器、生体試料充填装置、生体試料定量装置、及び生体試料反応方法
WO2012171983A3 (fr) * 2011-06-14 2013-05-10 Baxter International Inc. Procédé de production d'un produit polymérisé
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CN103826717A (zh) * 2011-07-28 2014-05-28 Q芯片有限公司 珠粒收集设备及珠粒收集方法
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CN102974255A (zh) * 2012-10-31 2013-03-20 中国科学院过程工程研究所 一种被动式螺旋微结构混合装置及应用
CN102974255B (zh) * 2012-10-31 2015-07-01 中国科学院过程工程研究所 一种被动式螺旋微结构混合装置及应用
CN105728071A (zh) * 2016-02-04 2016-07-06 中国地质大学（北京） 一种微流控芯片及其应用
CN106076218A (zh) * 2016-06-01 2016-11-09 苏州汶颢芯片科技有限公司 微流控芯片及碳量子点的合成方法
CN106076218B (zh) * 2016-06-01 2019-05-03 苏州汶颢芯片科技有限公司 微流控芯片及碳量子点的合成方法
CN107597033A (zh) * 2017-09-29 2018-01-19 东莞理工学院 一种弹簧管式柔性微化学反应器

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