Structurally ordered distributed polymers and methods for making the same

Abstract

This invention provides a polymer with an ordered distribution structure and its preparation method, belonging to the field of polymer preparation technology. This invention introduces a polymerizable ionic liquid into a polymer monomer. By applying a vertical electric and magnetic field, the ions in the ionic liquid undergo directional movement, forming an ordered distribution structure in the system where one end is enriched with the ionic liquid and the other end is enriched with the remaining monomers. The system is then solidified to construct the ordered polymer structure.

Description

Technical Field

[0001] This invention belongs to the field of polymer preparation technology, specifically relating to a polymer with an ordered distribution of structure and its preparation method. Background Technology

[0002] Polymer materials are widely used in fields such as electronic devices, biomedicine, and energy storage due to their advantages such as flexible molecular design, convenient processing, and low cost.

[0003] The macroscopic properties of polymers are directly determined by their microscopic ordered structure. However, the entanglement of polymer molecular chains and the uncontrollability of chain folding and phase separation during polymerization make it difficult for existing technologies to construct long-range, uniform, and defect-controllable ordered polymers.

[0004] Existing preparation methods are either complex and costly, or difficult to scale up; moreover, the resulting polymer structures lack sufficient order, limiting key properties such as charge transport efficiency and mechanical strength, thus failing to meet the application requirements of high-end devices. For example, self-assembly methods utilize intermolecular / intramolecular interactions (such as hydrogen bonds and van der Waals forces) to achieve self-assembly and form ordered structures, but are easily affected by molecular chain entanglement, making it difficult to control the degree of order and uniformity; template methods use inorganic nanoparticles, photolithographic patterns, etc., as templates to guide the directional alignment of polymer molecules, which can improve the order, but the template preparation / removal process is complex and costly, making it difficult to scale up; external force-induced methods use external forces such as stretching, shearing, electric fields, and magnetic fields to induce the directional alignment of polymer molecular chains, which is relatively simple to operate, but the structure is uncontrollable, prone to structural defects, and lacks long-range order; interface-induced methods utilize the interaction of the substrate interface to regulate the stacking of polymer molecules, which is suitable for thin-layer structural components, but has high requirements for the substrate and limited adaptability. Summary of the Invention

[0005] The purpose of this invention is to provide a polymer with an ordered structural distribution and a method for preparing the same. The preparation method provided by this invention is simple, scalable, and produces a polymer with an ordered and controllable structural distribution.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a polymer with an ordered structural distribution, comprising: A monomer solution is obtained by mixing a polymer monomer, an ionic liquid, and an initiator; the ionic liquid contains polymerizable groups in its molecular structure. An electric field and a magnetic field are simultaneously applied to the monomer solution, followed by photocuring to obtain a polymer with an ordered distribution of structure; the direction of the electric field is perpendicular to the direction of the magnetic field.

[0007] Preferably, the polymerizable groups in the ionic liquid molecular structure include vinyl, allyl, epoxy, or acrylate groups.

[0008] Preferably, the voltage of the electric field is 5~25V.

[0009] Preferably, the strength of the magnetic field is 100~1000mT.

[0010] Preferably, the mass ratio of the ionic liquid to the polymer monomer is (0.5~20):100.

[0011] Preferably, the mass ratio of the initiator to the polymer monomer is (0.5~5):100.

[0012] Preferably, the electric and magnetic fields are applied for 10 to 25 minutes.

[0013] Preferably, the photocuring time is 2 to 5 minutes.

[0014] Preferably, the polymer monomer is a photocurable monomer.

[0015] The present invention also provides a polymer with an ordered distribution of structure obtained by the preparation method described in the above technical solution.

[0016] This invention provides a method for preparing a polymer with an ordered distribution structure, comprising: mixing a polymer monomer, an ionic liquid, and an initiator to obtain a monomer solution; wherein the ionic liquid contains polymerizable groups in its molecular structure; simultaneously applying an electric field and a magnetic field to the monomer solution, followed by curing, to obtain a polymer with an ordered distribution structure; wherein the direction of the electric field is perpendicular to the direction of the magnetic field. This invention introduces a polymerizable ionic liquid into the polymer monomer, and by applying a perpendicular electric field and magnetic field, causes ions in the ionic liquid to move directionally, forming an ordered distribution structure in the system with one end enriched in the ionic liquid and the other end enriched in the remaining monomers. Then, photocuring is performed to construct the ordered polymer structure. Results from the embodiments show that the polymer prepared using the method provided by this invention has a significantly higher nitrogen content on the ionic liquid-enriched side than on the photocured monomer-enriched side; simultaneously, the contact angle value on the ionic liquid-enriched side is also significantly lower (due to the enrichment of hydrophilic ion pairs), significantly lower than the contact angle of the photocured monomer polymer, with a difference of more than 1° between the two sides. Attached Figure Description

[0017] Figure 1 The image shows a physical sample of Embodiment 2 of the present invention and the test sites for energy-dispersive X-ray spectroscopy analysis. Figure 2 EDS image of the polymer enrichment side of the polymer ionic liquid obtained in Example 2 of the present invention; Figure 3 This is an EDS image of the middle position of the polymer obtained in Example 2 of the present invention; Figure 4 This is an EDS image of the polymer enrichment side of the polymer photocurable monomer obtained in Example 2 of the present invention. Detailed Implementation

[0018] All raw materials used in this invention are not particularly limited in their source; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0019] There are no particular restrictions on the purity of any of the raw materials used in this invention. However, this invention preferably uses raw materials of industrial purity or conventional purity used in polymer preparation.

[0020] This invention provides a method for preparing a polymer with an ordered structural distribution, comprising: A monomer solution is obtained by mixing a polymer monomer, an ionic liquid, and an initiator; the ionic liquid contains polymerizable groups in its molecular structure. An electric field and a magnetic field are simultaneously applied to the monomer solution, followed by photocuring to obtain a polymer with an ordered distribution of structure; the direction of the electric field is perpendicular to the direction of the magnetic field.

[0021] This invention involves mixing polymer monomers, ionic liquids, and initiators to obtain a monomer solution.

[0022] In this invention, the polymer monomer is preferably a photocurable monomer. Photocurable monomers have the characteristic of fast curing speed, which can rapidly cure monomer solutions in different enrichment states.

[0023] In one embodiment of the present invention, the polymer monomer can be an acrylate monomer, an epoxy monomer, a vinyl ether monomer, or an N-vinyl monomer, specifically isobornyl acrylate, hydroxyethyl (meth)acrylate, dipropylene glycol diacrylate, 3,3-[oxybismethylene]-bis[3-ethyl]oxetane, 1,4-butanediol diglycidyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, or N-vinylpyrrolidone.

[0024] In one embodiment of the present invention, the initiator may be one or more of triphenylhexafluoroantimony thionium salt, triarylsulfonium hexafluoroantimony salt, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0025] In this invention, the preferred mass ratio of the initiator to the polymer monomer is (0.5~5):100, more preferably (1~3):100. As one embodiment of this invention, the mass ratio of the initiator to the polymer monomer can be 0.5:100, 0.8:100, 0.9:100, 1:100, 1.5:100, 1.8:100, 2:100, 2.5:100, 3:100, or 4:100. A mass ratio of initiator to polymer monomer within the above ranges is beneficial for constructing an ordered polymer structure.

[0026] In this invention, the ionic liquid contains polymerizable groups in its molecular structure. These polymerizable groups can polymerize with polymer monomers to form polymers, thus avoiding polymer structural defects that can occur when monomer solutions in different enrichment states polymerize.

[0027] In this invention, the polymerizable groups in the ionic liquid molecular structure preferably include vinyl, allyl, epoxy, or acrylate groups. These groups can all polymerize with polymer monomers, which helps to reduce structural defects in the polymer.

[0028] As one embodiment of the present invention, the main structure of the ionic liquid can be imidazole, pyridine, quaternary ammonium salt, quaternary phosphonium salt or acrylate; specifically, the ionic liquid can be an allylpropyl imidazole bromide ionic liquid or a methylpropyl imidazole bromide ionic liquid.

[0029] In this invention, the preferred mass ratio of the ionic liquid to the polymer monomer is (0.5~20):100, more preferably (1~10):100. As one embodiment of this invention, the mass ratio of the ionic liquid to the polymer monomer can be 0.5:100, 1:100, 2:100, 3:100, 5:100, 8:100, 10:100, or 15:100. A mass ratio of ionic liquid to polymer monomer within the above ranges is beneficial for constructing an ordered polymer structure.

[0030] The present invention does not have any particular limitation on the mixing, as long as the raw materials can be mixed evenly.

[0031] After obtaining the monomer solution, the present invention applies an electric field and a magnetic field to the monomer solution simultaneously, and then performs photocuring to obtain a polymer with an ordered distribution of structure.

[0032] In this invention, the direction of the electric field is perpendicular to the direction of the magnetic field. The electric field causes the anions and cations in the ionic liquid to move in opposite directions, but both are parallel to the direction of the electric field. Simultaneously, applying a magnetic field perpendicular to the direction of the electric field causes the anions and cations to experience forces in the same direction, pushing the ionic liquid as a whole to one side of the system, forming an ionic liquid enrichment region. As one embodiment of this invention, the direction of the electric field can be horizontal, and the direction of the magnetic field can be perpendicular to the ground. The ionic liquid will move along the horizontal direction perpendicular to the electric field, eventually enriching at one end of the system.

[0033] In this invention, the voltage of the electric field is preferably 5~25V, more preferably 10~20V; as one embodiment of this invention, the voltage of the electric field can be 6V, 8V, 10V, 12V, 14V, 15V, 16V, or 18V. A voltage within the above range is beneficial to the movement of anions and cations in the ionic liquid, forming monomer solutions with different enrichment states.

[0034] In this invention, the strength of the magnetic field is preferably 100-1000 mT, more preferably 200-600 mT; as one embodiment of this invention, the strength of the magnetic field can be 150 mT, 250 mT, 373 mT, 400 mT, 500 mT, 600 mT, 700 mT, 800 mT, or 900 mT. A magnetic field strength within the above range is beneficial for the movement of anions and cations in the ionic liquid under the influence of the Lorentz force, forming monomer solutions with different enrichment states.

[0035] In one embodiment of the present invention, the magnetic field can be provided by a magnet.

[0036] In this invention, the application time of the electric and magnetic fields is preferably 10-25 minutes, more preferably 15-20 minutes; as one embodiment of this invention, the application time of the electric and magnetic fields can be 10 minutes, 12 minutes, 15 minutes, 18 minutes, or 20 minutes. Application times within the above ranges are beneficial for the sufficient movement of the ionic liquid.

[0037] In one embodiment of the present invention, the monomer solution can be coated on a substrate, and then an electric field parallel to the substrate and a magnetic field perpendicular to the plane of the substrate are applied; the substrate can be a glass slide or a PP substrate.

[0038] In this invention, the photocuring time is preferably 2-5 minutes, more preferably 3-4 minutes. A photocuring time within this range is beneficial for the complete curing of the polymer.

[0039] In one embodiment of the present invention, the light source for photocuring can be an ultraviolet light source.

[0040] The present invention does not particularly limit the specific operation of the photocuring process; conventional photocuring methods in the art can be used to cure the monomer solution.

[0041] This invention introduces polymerizable ionic liquid into polymer monomers. By applying a vertical electric field and a magnetic field, the ions in the ionic liquid are directionally moved, forming an ordered distribution structure in the system with one end enriched with ionic liquid and the other end enriched with the remaining monomers. Then, photocuring is performed to construct an ordered polymer structure.

[0042] The present invention also provides a polymer with an ordered distribution of structure obtained by the preparation method described in the above technical solution.

[0043] The polymer provided by this invention exhibits different physicochemical properties at different locations of the polymer due to the different distribution states of the monomers, thereby meeting the needs of specific application scenarios.

[0044] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0045] Example 1 A method for preparing a polymer with an ordered structural distribution, comprising the following steps: Take 1g of 3,3-[oxydimethylene]-bis[3-ethyl]oxetane, 0.02g of allylpropylimidazolium bromide ionic liquid, and 0.005g of triarylsulfonium hexafluoroantimonate initiator, mix and dissolve to form a monomer solution; coat the monomer solution onto a glass slide, apply an electric field of 20V to both sides of the glass slide, place a magnet (373mT) above the glass slide, remove the electric field and magnet after 10min, introduce an ultraviolet curing light source above the glass slide, and cure for 3min to obtain a polymer with an ordered distribution of structure.

[0046] The obtained polymer was subjected to contact angle testing, and the contact angles at both ends of the polymer on the glass slide were 84.68° and 77.04°, respectively.

[0047] Example 2 A method for preparing a polymer with an ordered structural distribution, comprising the following steps: Take 1g of 3-hydroxymethyl-3-ethyloxetane, 0.02g of allylpropylimidazolium bromide ionic liquid, and 0.009g of triphenylhexafluoroantimony thionium carbonate initiator, mix and dissolve to form a monomer solution; coat the monomer solution onto a glass slide, apply an electric field of 15V to both sides of the glass slide, place a magnet (373mT) above the glass slide, and after 10min, introduce an ultraviolet curing light source above the glass slide and cure for 3min to obtain a polymer with an ordered distribution of structure.

[0048] The obtained polymer was subjected to contact angle testing, and the contact angles at both ends of the polymer on the glass slide were 70.43° and 68.75°, respectively.

[0049] The obtained polymer was subjected to energy-dispersive X-ray spectroscopy analysis, and the physical image and EDS plot are shown below. Figures 1-4 As shown. Figure 1 The three locations in the middle are the sites where tests were conducted. From Figures 2-4 It can be seen that the N content at the three sites is 4.02%, 1.25%, and 0.83% respectively, which also indicates that the content of ionic liquid at the three sites gradually decreases, confirming the ordered distribution structure of the polymer.

[0050] Example 3 A method for preparing a polymer with an ordered structural distribution, comprising the following steps: Take 1g of 3,3-[oxydimethylene]-bis[3-ethyl]oxetane, 0.03g of vinylpropyl imidazolium bromide ionic liquid, 0.004g of initiator triarylsulfonium hexafluoroantimonate, and 0.004g of 2-hydroxy-2-methyl-1-phenyl-1-propanone, mix and dissolve to form a monomer solution; coat the monomer solution onto a PP substrate, apply an electric field of 20V to both sides of the PP substrate, place a magnet (373mT) above a glass slide, and after 5min, introduce an ultraviolet curing light source above the PP substrate and cure for 3min to obtain a polymer with an ordered distribution of structure.

[0051] The obtained polymer was subjected to contact angle testing, and the contact angles at both ends of the polymer on the PP substrate were 63.04° and 61.79°, respectively.

[0052] Comparative Example 1 A method for preparing a polymer, comprising the following steps: Take 1g of 3,3-[oxydimethylene]-bis[3-ethyl]oxetane, 0.02g of allylpropylimidazolium bromide ionic liquid, and 0.005g of triarylsulfonium hexafluoroantimonate initiator, mix and dissolve to form a monomer solution; coat the monomer solution onto a glass slide, introduce an ultraviolet curing light source above the glass slide, and cure for 3min to obtain the polymer.

[0053] The obtained polymer was subjected to contact angle testing, and the contact angle of the polymer on the glass slide was 58.48°.

[0054] Comparative Example 2 A method for preparing a polymer, comprising the following steps: Take 1g of 3,3-[oxydimethylene]-bis[3-ethyl]oxetane, 0.02g of allylpropylimidazolium bromide ionic liquid, and 0.005g of triarylsulfonium hexafluoroantimonate initiator, mix and dissolve to form a monomer solution; coat the monomer solution onto a glass slide, apply a 20V electric field to both sides of the glass slide, remove the electric field after 10min, introduce an ultraviolet curing light source above the glass slide, and cure for 3min to obtain the polymer.

[0055] The obtained polymer was subjected to contact angle testing, and the contact angles at both ends of the polymer on the glass slide were 57.68° and 57.46°, respectively.

[0056] Comparative Example 3 A method for preparing a polymer, comprising the following steps: Take 1g of 3,3-[oxydimethylene]-bis[3-ethyl]oxetane, 0.02g of allylpropylimidazolium bromide ionic liquid, and 0.005g of triarylsulfonium hexafluoroantimonate initiator, mix and dissolve to form a monomer solution; coat the monomer solution onto a glass slide, place a magnet (373mT) above the glass slide, remove the magnet after 10min, introduce an ultraviolet curing light source above the glass slide, and cure for 3min to obtain the polymer.

[0057] The obtained polymer was subjected to contact angle testing, and the contact angles at both ends of the polymer on the glass slide were 58.35° and 58.06°, respectively.

[0058] As can be seen from the above embodiments and comparative examples, the present invention introduces both electric and magnetic fields, which can prepare polymers with ordered structural distribution. Moreover, the preparation method provided by the present invention is simple, requires no complex equipment, and is easy to scale up for production.

[0059] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a polymer with an ordered structural distribution, comprising: The polymer monomer, ionic liquid, and initiator are mixed to obtain a monomer solution; The molecular structure of the ionic liquid contains polymerizable groups; An electric field and a magnetic field are simultaneously applied to the monomer solution, followed by photocuring to obtain a polymer with an ordered distribution of structure; the direction of the electric field is perpendicular to the direction of the magnetic field.

2. The preparation method according to claim 1, characterized in that, The polymerizable groups in the molecular structure of the ionic liquid include vinyl, allyl, epoxy, or acrylate groups.

3. The preparation method according to claim 1, characterized in that, The voltage of the electric field is 5~25V.

4. The preparation method according to claim 1 or 3, characterized in that, The strength of the magnetic field is 100~1000mT.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the ionic liquid to the polymer monomer is (0.5~20):

100.

6. The preparation method according to claim 1, characterized in that, The mass ratio of the initiator to the polymer monomer is (0.5~5):

100.

7. The preparation method according to claim 1, characterized in that, The electric and magnetic fields are applied for 10 to 25 minutes.

8. The preparation method according to claim 1, characterized in that, The photocuring time is 2-5 minutes.

9. The preparation method according to claim 1, characterized in that, The polymer monomer is a photocurable monomer.

10. A polymer with an ordered distribution of structure obtained by the preparation method according to any one of claims 1 to 9.

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