CN104695052A - Preparation method for spherical cavity equipped polymer fiber and special microfluidic chip - Google Patents

Preparation method for spherical cavity equipped polymer fiber and special microfluidic chip Download PDF

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Publication number
CN104695052A
CN104695052A CN201310657245.7A CN201310657245A CN104695052A CN 104695052 A CN104695052 A CN 104695052A CN 201310657245 A CN201310657245 A CN 201310657245A CN 104695052 A CN104695052 A CN 104695052A
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solution
polymer fiber
passage
channel
continuous phase
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CN104695052B (en
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秦建华
于跃
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a preparation method for a spherical cavity equipped polymer fiber and a special microfluidic chip. With the chip and the method, polymer fiber with a diameter ranging from micron level to millimeter level can be prepared. Spacing and size controllable spherical cavities can continuously be formed in the polymer fiber, and various inclusions can be loaded in the cavities. The method combines a droplet microfluidic technology and a spinning microfluidic technology, utilizes the droplet microfluidic technology to disperse a volatile liquid uniformly in the continuous flow of a polymer monomer solution in the form of droplets, and utilizes the spinning microfluidic technology to form polymer fiber and arrange the droplets therein orderly. The droplet solution is removed from solidified polymer fiber by means of its volatilization characteristic so as to form the spherical cavities with uniform and controllable size and adjustable spacing. The substances added into the droplets in advance can be loaded into the fiber cavities, and the material can be endowed with flexible performance so as to be expected for application in wide fields.

Description

A kind of method and micro-fluidic chip special preparing tool spherical hollow space polymer fiber
Technical field
The invention belongs to the crossing domain of new material technology and microflow control technique, be specifically related to a kind of method and the micro-fluidic chip special of preparing tool spherical hollow space polymer fiber.
Background technology
The present invention relies on.Micro-fluidic chip (microfluidic chip) is also known as chip lab (lab on a chip), referring to a Routine Test Lab basic operation unit is integrated on the chip of a piece several square centimeters (even less), network is formed by microchannel, whole system is run through, in order to replace a kind of technology of the various functions of Routine Test Lab with controlled fluid.Drop is micro-fluidic is an important branch of microfluidic chip technology.It utilizes two phase flow to form monodispersed water droplet or oil droplet in the microfluidic channel of T-shaped or forms such as folder stream etc.Monodispersed drop is that high-throughout micro-analysis inspection and granular materials synthesis provide a powerful support.
High molecular polymer refers to be repeated by many identical, simple construction units the high-molecular weight compounds that is formed by connecting by covalent bond.The compound be made up of the Small molecular that can form construction unit is called monomer, is the raw material of synthetic polymer.Because macromolecule polymer material has more various more excellent characteristic relative to traditional material, the popularity of therefore its development speed and application greatly exceed traditional material.Can say that macromolecular material has become the important materials in the fields such as industry, agricultural, national defence and science and technology.One large characteristic of macromolecular material is that it can be processed into the material of various form according to demand easily, such as bar-shaped, particle, fiber etc.But with regard to high polymer fiber, due to the restriction of processing method, be difficult to prepare the fibrous material with more complicated specific form and composition.Along with the development of science and technology, the requirement of every field to material property and function improves gradually.Prepare more complicated and polymorphic, multicomponent multifunction polymeric material, especially polymeric fibre material becomes the task of top priority.
Summary of the invention
The object of this invention is to provide a kind of method and special chip thereof based on microflow control technique preparation with the polymer fiber of spherical hollow space structure, utilize chip provided by the present invention and method, the polymer fiber with special spherical hollow space can be prepared, size range can from micron order to grade, type of polymer is various, spherical hollow space spacing and size adjustable, and many kinds of substance can be forgiven in cavity.The application prospect of the polymer fiber of this type of tool replicated architecture and composition is extensive.
The invention provides a kind of micro-fluidic chip, this micro-fluidic chip is divided into two-layer, and materials at two layers surface all has channel design, and two channel designs are Mirror Symmetry, and layers of chips material is sealed when two Mirror Symmetry channel designs overlap;
This chip have one for introduce the continuous phase entrance of polymer monomer solution and passage, one for introduce the decentralized photo entrance of drop decentralized photo solution and passage, one for introducing the entrance of sheath stream solution and passage, the folder circulation road construction unit for generation of drop, the spout structure unit for generation of polymer fiber, a polymer fiber produces passage and a collection of products outlet.
Micro-fluidic chip provided by the invention, described folder circulation road structure is positioned at the upstream of spout structure, is the intersection of continuous phase solution passage and decentralized photo solution channel, in cross.
Micro-fluidic chip provided by the invention, described spout structure unit is positioned at the downstream of folder circulation road construction unit, is the intersection that continuous phase solution passage, sheath stream solution channel and polymer fiber form passage three; Continuous phase solution passage and polymer fiber form passage in distributing up and down, have common central shaft; Polymer fiber forms channel diameter and is greater than continuous phase solution passage; Sheath stream solution channel is divided into two branch roads, is positioned at the left and right sides of spout structure unit.
Micro-fluidic chip provided by the invention, described collection of products outlet is positioned at the end that polymer fiber forms passage, is communicated with chip channel and external environment.
Present invention also offers the method based on described micro-fluidic chip preparation with the polymer fiber of spherical hollow space structure, utilize syringe pump, by decentralized photo solution (volatile liquid material), continuous phase solution (polymer monomer solution), sheath stream solution (the third liquid substance) is injected into the decentralized photo solution channel of micro-fluidic chip respectively by respective entrance, in continuous phase solution passage and sheath stream solution channel; Adjust the flow velocity of each fluid in suitable scope, each solution is made to flow through folder circulation road construction unit and spout structure unit respectively, and when each solution flows through polymer fiber formation passage, channel interior or outside apply suitable polymerizing condition, aggregate into fiber to make polymer monomer; Subsequently in the collection of products exit of chip and continuablely collect the polymeric fibre material including drop; By the outer sheath stream solution of polymeric fibre material collected and internal residual removal of solvents, utilize the volatility of droplet solution it to be removed from polymer fiber afterwards, the polymer fiber with spherical hollow space can be formed; By adding certain material in advance in drop decentralized photo solution, this material can be forgiven in the spherical hollow space of polymer fiber, to give this fibrous material special performance.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, and at described folder circulation road construction unit place, decentralized photo solution can form drop automatically and be forgiven in continuous phase solution, and is carried to the spout structure unit in downstream.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, at described spout structure unit place, the continuous phase solution and the sheath stream solution continuous print that are loaded with drop import polymer fiber generation passage from respective passage, defining inner is polymer monomer solution, and outside is the sheath stream flow pattern of sheath stream solution.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, suitable polymerizing condition is applied in described polymer fiber formation channel interior or outside, polymer monomer is polymerized at sheath stream internal layer continuous print, form the inner polymeric fibre material including drop, and export pass-out to chip exterior for collection by collection of products under the carrying of sheath stream.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, by the outer sheath stream solution of polymeric fibre material collected and internal residual removal of solvents, the volatility of droplet solution is utilized it to be removed from polymer fiber afterwards, to form the polymer fiber with spherical hollow space.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, the flow velocity of decentralized photo and continuous phase solution is regulated by described syringe pump, to regulate size and the spacing of the drop generated, and then control size and the spacing of polymer fiber inner spherical cavity.
Preparation provided by the invention has the method for the polymer fiber of spherical hollow space structure, by adding certain material in advance in drop decentralized photo solution, this material can be forgiven in the spherical hollow space of polymer fiber, to give this fibrous material special performance.
The present invention has the following advantages:
(1) simple to operate, preparation process is stablized;
(2) polymerization is flexible, fibrous material wide variety;
(3) the large Small Distance of spherical hollow space is adjustable;
(4) various material can be forgiven in cavity, the performance that fibrous material is special can be given.
Accompanying drawing explanation
Fig. 1: the chip schematic diagram be made up of the two-layer polymeric material with Mirror Symmetry channel design, (A) is chip upper strata, and (B) is chip lower floor;
Fig. 2: stereo channel structural representation, comprising decentralized photo solution inlet (I1) and passage (D) thereof, continuous phase solution entrance (I2) and passage (C) thereof, sheath stream solution inlet (I3) and passage (S) thereof, polymer fiber forms passage (G), and collection of products outlet (O);
Fig. 3: folder circulation road construction unit (CJ) and spout structure unit (SO) enlarged diagram; Two structures are respectively used to form drop and form sheath stream flow pattern.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1: chip structure of the present invention
Micro-fluidic chip of the present invention is divided into two-layer, and materials at two layers surface all has channel design, and two channel designs are Mirror Symmetry, and layers of chips material is sealed when two Mirror Symmetry channel designs overlap; Wherein, chip comprises the entrance of continuous phase solution and passage, the entrance of decentralized photo solution and passage, the entrance of sheath stream solution and passage, folder circulation road construction unit, spout structure unit, polymer fiber produce passage, collection of products outlet.
Described folder circulation road structure is positioned at the upstream of spout structure, is the intersection of continuous phase solution passage and decentralized photo solution channel, in cross.
Described spout structure unit is positioned at the downstream of folder circulation road construction unit, is the intersection that continuous phase solution passage, sheath stream solution channel and polymer fiber form passage three; Continuous phase solution passage and polymer fiber form passage in distributing up and down, have common central shaft; Polymer fiber forms channel diameter and is greater than continuous phase solution passage; Sheath stream solution channel is divided into two branch roads, is positioned at the left and right sides of spout structure unit.
Described collection of products outlet is positioned at the end that polymer fiber forms passage, is communicated with chip channel and external environment.
Embodiment 2:
Chip of the present invention is utilized to form single dispersing drop and sheath stream flow pattern
Utilize syringe pump, by non-polar solven X(decentralized photo solution), polar solvent Y solution (continuous phase solution), and non-polar solven Z(sheath stream solution) be injected into the decentralized photo solution channel of micro-fluidic chip respectively by respective entrance, in continuous phase solution passage and sheath stream solution channel.Adjust the flow velocity of each fluid in suitable scope.Can examine under a microscope, when solvent X is when flowing through folder circulation road construction unit, is dispersed into drops by solvent Y, and is carried to the spout structure unit place in downstream by solvent Y continuous print.When solvent Y by continuous phase solution passage through spout structure unit flow into polymer fiber form passage time, inside is wrapped in by the solvent Z flowing into this passage equally, form sheath stream flow pattern, and be carried to collection of products outlet by sheath stream solution solvent Z, finally flow out chip together.The drop can observing solvent X is inner at solvent Y all the time.Until be excluded chip.Regulate syringe pump to strengthen the flow velocity of solvent X, the drop that can be observed solvent X becomes large, pitch smaller.Regulate syringe pump to strengthen the flow velocity of solvent Y, the drop that can be observed solvent X diminishes, and spacing becomes large.
Prepare the calcium alginate hydrogel fiber of tool spherical hollow space
Using 1%(w/w) sodium alginate aqueous solution as continuous phase, HFE-7100 fluorocarbon oil as decentralized photo, 1%(w/w) anhydrous calcium chloride aqueous solution sheath stream phase the most, be passed in micro-fluidic chip of the present invention respectively by respective entrance and passage.Sodium alginate soln meets with sheath stream anhydrous chlorides of rase calcium solution after being passed into polymer fiber formation passage, and calcium ion and sodium alginate interact, and form solid-state calcium alginate fibre.HFE-7100 fluorocarbon oil solution is wrapped in calcium alginate fibre with the form of drop.The calcium alginate fibre being enclosed with fluorocarbon oil drop is collected by from collection exit and is wrapped on glass bar.Glass bar is placed in air, and the moisture in calcium alginate hydrogel can volatilize away, leaves drying and contracted calcium alginate fibre.After moisture evaporation is clean, high-volatile HFE-7100 starts to volatilize to air in silk, and in 1 ~ 2 minutes, HFE-7100 is totally volatilizable, in calcium alginate fibre, form spherical hollow space.

Claims (9)

1. a micro-fluidic chip, it is characterized in that: this micro-fluidic chip is divided into two-layer, materials at two layers surface all has channel design, and two channel designs are Mirror Symmetry, and layers of chips material is sealed when two Mirror Symmetry channel designs overlap;
Described chip comprises the entrance of continuous phase solution and passage, the entrance of decentralized photo solution and passage, the entrance of sheath stream solution and passage, folder circulation road construction unit, spout structure unit, polymer fiber produce passage, collection of products outlet.
2. according to micro-fluidic chip described in claim 1, it is characterized in that: described folder circulation road structure is positioned at the upstream of spout structure, is the intersection of continuous phase solution passage and decentralized photo solution channel, in cross.
3. according to micro-fluidic chip described in claim 1, it is characterized in that: described spout structure unit is positioned at the downstream of folder circulation road construction unit, is the intersection that continuous phase solution passage, sheath stream solution channel and polymer fiber form passage three; Continuous phase solution passage and polymer fiber form passage in distributing up and down, have common central shaft; Polymer fiber forms channel diameter and is greater than continuous phase solution passage; Sheath stream solution channel is divided into two branch roads, is positioned at the left and right sides of spout structure unit.
4. according to micro-fluidic chip described in claim 1, it is characterized in that: described collection of products outlet is positioned at the end that polymer fiber forms passage, is communicated with chip channel and external environment.
5. based on micro-fluidic chip preparation described in claim 1, there is the method for the polymer fiber of spherical hollow space structure, it is characterized in that: utilize syringe pump, by decentralized photo solution, continuous phase solution, sheath stream solution is injected into the decentralized photo solution channel of micro-fluidic chip respectively by respective entrance, in continuous phase solution passage and sheath stream solution channel; Adjust the flow velocity of each fluid in suitable scope, each solution is made to flow through folder circulation road construction unit and spout structure unit respectively, and when each solution flows through polymer fiber formation passage, channel interior or outside apply suitable polymerizing condition, aggregate into fiber to make polymer monomer; Subsequently in the collection of products exit of chip and continuablely collect the polymeric fibre material including drop; By the outer sheath stream solution of polymeric fibre material collected and internal residual removal of solvents, utilize the volatility of droplet solution it to be removed from polymer fiber afterwards, the polymer fiber with spherical hollow space can be formed.
6. there is according to preparation described in claim 5 method of the polymer fiber of spherical hollow space structure, it is characterized in that: at described folder circulation road construction unit place, decentralized photo solution can form drop automatically and be forgiven in continuous phase solution, and is carried to the spout structure unit in downstream.
7. there is according to preparation described in claim 5 method of the polymer fiber of spherical hollow space structure, it is characterized in that: at described spout structure unit place, the continuous phase solution and the sheath stream solution continuous print that are loaded with drop import polymer fiber generation passage from respective passage, defining inner is polymer monomer solution, and outside is the sheath stream flow pattern of sheath stream solution.
8. there is according to preparation described in claim 5 method of the polymer fiber of spherical hollow space structure, it is characterized in that: apply suitable polymerizing condition in described polymer fiber formation channel interior or outside, polymer monomer is polymerized at sheath stream internal layer continuous print, form the inner polymeric fibre material including drop, and export pass-out to chip exterior for collection by collection of products under the carrying of sheath stream.
9. there is according to preparation described in claim 5 method of the polymer fiber of spherical hollow space structure, it is characterized in that: the flow velocity being regulated decentralized photo and continuous phase solution by described syringe pump, to regulate size and the spacing of the drop generated, and then control size and the spacing of polymer fiber inner spherical cavity.
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Cited By (13)

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CN105797791A (en) * 2016-03-16 2016-07-27 清华大学深圳研究生院 Microfluid ion source chip and preparation method thereof
CN106245134A (en) * 2016-06-29 2016-12-21 东华大学 A kind of spinning process that micro-fluid chip is used for recombinant spider silk proteins
CN108149334A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 The method and special chip of complicated form microfibre are prepared based on micro-fluidic chip
CN108149342A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 The preparation method of Composite Hollow microfibre based on microflow control technique
CN108770348A (en) * 2015-12-14 2018-11-06 美国因迪森光学技术有限责任公司 Nanoemulsions optical material
CN109027688A (en) * 2018-10-26 2018-12-18 郑州大学 A kind of low pressure fluid path integrated package and its processing technology
CN109652359A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of preparation method of the cell 3D culture hydrogel microsphere based on aqueous two-phase drop
CN109652310A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of simple controllable method for preparing of the groove microfilament based on microflow control technique
CN109891009A (en) * 2016-06-23 2019-06-14 香港大学 For manufacturing chamber-microfibre, the method and apparatus of microfibre, line and silk
CN111250009A (en) * 2018-12-03 2020-06-09 成都市银隆新能源有限公司 Method for preparing lithium ion battery material by using microfluidic technology
CN112853510A (en) * 2019-11-28 2021-05-28 中国科学院大连化学物理研究所 Controllable preparation method of inner groove microfilament based on microfluidic technology
CN113355754A (en) * 2021-07-07 2021-09-07 中国计量大学 Method for preparing multiphase fiber based on microfluidic-electrostatic spinning technology
CN114149893A (en) * 2021-11-23 2022-03-08 中国科学院青岛生物能源与过程研究所 Particle self-clamping flow type micro-fluidic chip, manufacturing method thereof and particle self-dispersion method

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CN108770348A (en) * 2015-12-14 2018-11-06 美国因迪森光学技术有限责任公司 Nanoemulsions optical material
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CN105797791B (en) * 2016-03-16 2017-11-03 清华大学深圳研究生院 A kind of microfluid ion source chip and preparation method thereof
CN105797791A (en) * 2016-03-16 2016-07-27 清华大学深圳研究生院 Microfluid ion source chip and preparation method thereof
CN109891009A (en) * 2016-06-23 2019-06-14 香港大学 For manufacturing chamber-microfibre, the method and apparatus of microfibre, line and silk
CN106245134A (en) * 2016-06-29 2016-12-21 东华大学 A kind of spinning process that micro-fluid chip is used for recombinant spider silk proteins
CN106245134B (en) * 2016-06-29 2018-05-25 东华大学 A kind of spinning process that micro-fluid chip is used for recombinant spider silk proteins
CN108149334A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 The method and special chip of complicated form microfibre are prepared based on micro-fluidic chip
CN108149342A (en) * 2016-12-05 2018-06-12 中国科学院大连化学物理研究所 The preparation method of Composite Hollow microfibre based on microflow control technique
CN108149342B (en) * 2016-12-05 2020-05-19 中国科学院大连化学物理研究所 Preparation method of composite cavity microfiber based on microfluidic technology
CN109652359A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of preparation method of the cell 3D culture hydrogel microsphere based on aqueous two-phase drop
CN109652310A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of simple controllable method for preparing of the groove microfilament based on microflow control technique
CN109027688A (en) * 2018-10-26 2018-12-18 郑州大学 A kind of low pressure fluid path integrated package and its processing technology
CN111250009A (en) * 2018-12-03 2020-06-09 成都市银隆新能源有限公司 Method for preparing lithium ion battery material by using microfluidic technology
CN112853510A (en) * 2019-11-28 2021-05-28 中国科学院大连化学物理研究所 Controllable preparation method of inner groove microfilament based on microfluidic technology
CN112853510B (en) * 2019-11-28 2022-05-10 中国科学院大连化学物理研究所 Controllable preparation method of inner groove microfilament based on microfluidic technology
CN113355754A (en) * 2021-07-07 2021-09-07 中国计量大学 Method for preparing multiphase fiber based on microfluidic-electrostatic spinning technology
CN114149893A (en) * 2021-11-23 2022-03-08 中国科学院青岛生物能源与过程研究所 Particle self-clamping flow type micro-fluidic chip, manufacturing method thereof and particle self-dispersion method

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