CN115594858B - Dynamic soft material capable of continuously growing and preparation method and application thereof - Google Patents
Dynamic soft material capable of continuously growing and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000000463 material Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 32
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- -1 biology Substances 0.000 claims abstract description 3
- 239000008204 material by function Substances 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
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- 125000000524 functional group Chemical group 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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Abstract
The invention provides a dynamic soft material capable of continuously growing, a preparation method and application thereof, wherein a first monomer and a second monomer which can form a supermolecular structure are selected, one monomer is polymerized to form a polymer, and a seed material is formed after the other monomer is polymerized by simple swelling, so that the dynamic soft material can be obtained by continuous and repeated growth of the seed material. The performance of the dynamic soft material can realize large-scale regulation and control in the growth process, and the material can also be used as a base material, and after other functional materials are added, the growth of the multifunctional material is realized. The continuously-growing dynamic soft material has the advantages of excellent biocompatibility, large-scale adjustable mechanical property, fixed-point growth, shape control, controllable growth and the like, has wide application prospect in the aspects of bionic materials, biology, medicine and the like, has simple and easy synthesis process, wide application range and low preparation cost, and is easy to popularize.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a dynamic soft material capable of continuously growing, a preparation method and application thereof.
Background
Hydrogel materials, which are one of dynamic soft materials, are widely used in the fields of tissue engineering, biology, medicine, etc. because of their high water content, excellent biocompatibility, etc. With the introduction of various mechanisms, the mechanical properties of the material are greatly enhanced, the material becomes more similar to biological tissues, and the material has great application value in the field of biological tissues. However, the material is an excellent material with great application value, and has the defects that the material cannot realize adaptive growth like biological tissues and cannot be obviously changed according to requirements, so that the applicability of the dynamic soft material is limited.
Based on this, some work has been done to achieve adaptive growth of hydrogels. For example, gong et al developed a force-stimulated self-growing hydrogel material (Science 2019, 363:504-508.) although this material achieved force-stimulated self-growth, the drawbacks were evident: firstly, because it is a double-network hydrogel based on covalent bond crosslinking, the number of growth times is limited, and only 5 times of growth can be realized; and secondly, the size growth is limited, and the size self-adaptive growth cannot be realized. In addition, some work has been directed to introducing trithiocarbonate structures into materials (ACS cent. Sci.2017,3:124-134; adv. Mater.2015,27,8007-8010;ACS Macro Lett.2018,7,745-750) to enable multiple growth under photoinitiation, but while such materials are beneficial for growth, there are also problems: for example, the synthesis difficulty is high, special custom-made synthetic monomers are required, and the problem of initiator residues exists in the system, so that the finally presented growing material still contains dye-based initiator; in addition, the growing sites are positioned at the crosslinking positions, and the growing process sites are positioned at the crosslinking positions, so that the controllability is poor. Obviously, these materials have limited utility.
Some soft materials capable of continuously growing have been developed, and the preparation of the growing materials is realized through the rupture of chemical bonds. While these materials can effectively address the growth problem, the high energy required for the breaking of chemical bonds remains a challenge in terms of sustainable growth. Therefore, there is a need for a continuously growing soft material that is simple to prepare, readily available in raw materials, economical, and has little environmental impact and excellent performance.
Disclosure of Invention
The invention aims to provide a dynamic soft material capable of continuously growing, a preparation method and application thereof, and the material solves the problem that the prior art lacks an effective dynamic soft material with continuous growth and adaptive growth based on supermolecule acting force, and has the effects of simple preparation, easily available raw materials, economy and small influence on environment.
In order to solve the technical problems, the technical scheme provides the following steps:
in a first aspect, the present solution provides a method for preparing a continuously growing dynamic soft material, comprising the steps of:
s1, placing a first type of monomer into an aqueous solution, adding an initiator with the content of 0.2% mol, and polymerizing to obtain a polymer;
s2: placing a second type of monomer into an aqueous solution, adding an initiator with corresponding concentration to obtain a monomer solution, adding the monomer solution into the polymer prepared in the step S1, and obtaining a seed material in a polymerization mode, wherein the first type of monomer and the second type of monomer are polymerized into a supermolecular structure;
s3, subjecting the seed material prepared in the step S2 to at least one growth cycle to obtain a growth material, wherein the process of each growth cycle is as follows: adding the first type monomer containing the initiator into the seed material or the growth material obtained in the previous step, swelling the first type monomer containing the initiator, and polymerizing to obtain the growth material after growth, wherein the addition amount of the first type monomer is equal to the mass of the first type monomer in the step S1, continuing adding the corresponding second type monomer containing the initiator, swelling the second type monomer containing the initiator, and polymerizing to obtain the growth material serving as the growth material, wherein the addition amount of the second type monomer is equal to the mass of the second type monomer in the step S2.
Preferably, the first type of monomer may be selected from one or a combination of the following molecular structures;
the second type of monomer may be selected from one or a combination of the following molecular structures:
wherein:
preferably, when the first monomer is of an acid structure, the second monomer is of a basic structure; when the first monomer is in an ionic structure, the second monomer is in a quaternary ammonium salt structure.
Preferably, when the first type of monomer is in an acid structure, the second type of monomer selects a basic structure such as tertiary ammonia.
Preferably, the solution of S1-S3 contains the corresponding monomers and initiator in a molar ratio of 1:0.0005-0.005.
Preferably, the supermolecule functional group in the first type monomer in S1 and S3 can be one or more of carboxyl, sulfonic acid group, sodium carboxylate and sodium sulfonate.
Preferably, the supermolecular functional group in the second type of monomer in S2 and S3 can be one or more of amino, tertiary ammonia and quaternary ammonium salt.
Preferably, the initiator in S1-S3 is a water-soluble thermal initiator, wherein the thermal initiator is one of azo, peroxide and polysulfide.
Preferably, the initiator in S1-S3 is a water-soluble photoinitiator, wherein the photoinitiator is one of alpha-ketoglutaric acid and photoinitiator 2959.
In the growth process, the mass ratio of the first type monomer to the second type monomer is 1:0.1 to 10. Preferably, the mass ratio of the first type monomer to the second type monomer is 1:1.
Preferably, the amount of subsequent monomer added during the growth cycle is 100% by weight of the amount of the corresponding monomer during the preparation. Namely, the addition amount of the first type monomer or the second type monomer added in the growth cycle process is the same as that of the first type monomer or the second type monomer when preparing the seed material.
Preferably, when the initiator is a water-soluble thermal initiator, the free radical polymerization is carried out under thermal conditions, the thermal initiation being carried out at 40-90℃for 5-20h. Preferably, the conditions of thermal initiation are 40-90℃for 10 hours.
Preferably, when the initiator is a water-soluble photoinitiator, the polymerization of the free radicals is carried out under light-induced conditions, such as ultraviolet light reaction for 5-20 hours. Preferably, the photoinitiation conditions are ultraviolet light reaction for 8 hours.
The dynamic soft material that this scheme provided realizes many times growth through supermolecule functional group, and specifically, the dynamic soft material of this scheme realizes growing through two modes: the first growth mode is: preparing a polymer of a first type monomer containing a supermolecular functional group, polymerizing the polymer and a second type monomer with a corresponding supermolecular functional group, and then realizing the things-to-things crosslinking of the supermolecular function to prepare the seed material. The second type of growth mode is: after the first step of growth is realized by adding the solution containing the monomer for swelling polymerization, the polymer in the original polymer system is reconfigured by using the corresponding monomer with the supermolecular functional group for swelling polymerization, so as to realize the growth of the polymer.
The invention realizes multiple unlimited growth of materials by utilizing the breaking and recombination of the acting force of supermolecules. The specific mechanism is as follows: the prepared seed is physically crosslinked by utilizing the structure of the supermolecular functional group, so that a stable seed material is obtained; the method is characterized in that a monomer is introduced to swell on the basis of the original method, the swelled monomer can promote the dissociation and reconstruction of the original polymer structure, the inner polymer is reconfigured after the corresponding super-molecular functional group monomer is swelled and polymerized, the reconstructed polymer structure is fixed after polymerization, and the structure of the growth material which is reconfigured and fixed is stable. The reconstruction of this internal structure of the dynamic soft material of the present solution ensures that the material can achieve both growth without changing its shape and growth with a controllable shape.
The method can further grow corresponding monomers, can continue the process and finally form a structure similar to seeds, so that the finally obtained growth material can maintain unchanged performance, can realize large-scale controllable tuning of the performance and realize continuous growth.
Preferably, the properties of the material can be controlled over a wide range as monomers change during growth. The specific regulation and control are as follows: when the ratio of the first type monomer to the second type monomer is fixed in the growth process, the performance of the first type monomer can be kept unchanged; when the same type of monomer or the ratio of the two monomers is changed during continuous growth, the performance of the super-molecular structure is obviously reduced because the internal super-molecular structure is not similar to the distribution structure in the seed material; when other types of hard monomers are selected (e.g., the backbone bears methyl groups after polymerization), their properties can be significantly improved. Thus, according to the means described above, a large range of controllable tuning of the growth material can be achieved.
From the above, the invention is realized by the growth on the basis of non-covalent bonds, which can realize controllable growth and injection growth of fixed-point areas.
Preferably, in step S3, the monomer solution containing the initiator is injected into the localized area of the seed material or growth material obtained in the previous step.
In addition, the method realizes growth by utilizing a simple polymerizable structure, and can realize control of material properties and shapes in the growth process by simply modifying the grown monomers or components, thereby realizing effective control of the properties and shapes of the subsequently grown materials in situ. Although effective regulation of properties can be achieved at the preparation stage, in practical applications, later in-situ regulation of properties and shape is often required. The growth control properties and shape are therefore more advantageous in practical applications. Mainly it does not require re-preparation and replacement of the sample making the operation simpler.
In addition, the method contains a large number of structures such as carboxyl, sulfonic acid group, amino, tertiary ammonia, quaternary ammonium salt and the like in the growth material, and can be effectively combined with other substrates, so that the problem of dispersion of the growth material and the substrate material is effectively solved.
In a second aspect, the present disclosure provides a continuously-growing dynamic soft material, which is prepared according to the above-mentioned method for preparing a continuously-growing dynamic soft material.
Preferably, the dynamic soft material provided by the scheme can be combined with different substrates.
Preferably, functional materials such as color-changing materials, fluorescent materials, photo-thermal materials, conductive materials and the like are mixed in the base material, so that the functional composite soft material with in-situ growth control performance can be prepared.
In a third aspect, the present solution provides the use of a continuously growing dynamic soft material for the preparation of a functional material.
Compared with the prior art, the scheme has the following beneficial effects:
1. the continuously growing dynamic soft material has adjustable molecular structure and composition, and can effectively realize unlimited sustainable growth and later-stage in-situ regulation and control of the prepared material performance.
2. The continuously grown dynamic soft material of the present invention has excellent biocompatibility.
3. The continuously grown dynamic soft material can realize effective control of the material structure, control the shape change in situ and realize the adaptive growth of the material shape.
4. The preparation method of the continuously growing dynamic soft material has the advantages of simple and feasible process, environmental protection, high yield, low preparation cost and easy popularization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a physical view of a continuously growing dynamic soft material of the present invention;
FIG. 2 is a schematic diagram of the structure of supermolecules in a continuously growing dynamic soft material according to the present invention;
FIG. 3 is a scanning electron microscope image of a continuously growing dynamic soft material of the present invention.
FIG. 4 is a real image of a continuously growing dynamic soft material
FIG. 5 is a graph of mechanical properties of a continuously grown dynamic soft material seed and a post-growth material of the present invention;
FIG. 6 is a graph of the post performance control of a continuously growing dynamic soft material of the present invention;
FIG. 7 is a plot of the finite field growth of a continuously growing dynamic soft material of the present invention;
FIG. 8 is an injection growth chart of a continuously growing dynamic soft material according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The preferred embodiment of the invention provides a preparation method of a dynamic soft material capable of continuously growing, which comprises the following specific steps:
and (3) selecting a first type of monomer: acrylic acid; and (3) selecting a second type of monomer: dimethylaminoethyl methacrylate; and (3) selecting a photoinitiator: alpha-ketoglutaric acid.
The preparation method comprises the following steps:
5g of acrylic acid and 20mg of alpha-ketoglutaric acid are added into 5g of water, mixed evenly and polymerized for 8 hours under an ultraviolet lamp, thus obtaining the polymer.
Taking 5g of dimethylaminoethyl methacrylate and 9mg of alpha-ketoglutaric acid, adding into 5g of water, uniformly mixing, adding the mixed solution into the prepared polymer 1, standing overnight, and then placing under an ultraviolet lamp for polymerization for 8 hours to obtain a dynamic soft material, namely the seed 1. The physical diagram of the seed 1 is shown in fig. 1, and the scanning electron microscope diagram is shown in fig. 3.
Example 2:
the preferred embodiment of the invention provides a preparation method of a dynamic soft material capable of continuously growing, which comprises the following specific steps:
and (3) selecting a first type of monomer: acrylic acid; and (3) selecting a second type of monomer: dimethylaminoethyl methacrylate; and (3) selecting a photoinitiator: alpha-ketoglutaric acid.
10g of acrylic acid and 40mg of alpha-ketoglutaric acid are added into 10g of water, mixed evenly and polymerized for 8 hours under an ultraviolet lamp, thus obtaining the polymer.
Taking 5g of dimethylaminoethyl methacrylate and 9mg of alpha-ketoglutaric acid, adding into 5g of water, uniformly mixing, adding the mixed solution into the prepared polymer 1, standing overnight, and then placing under an ultraviolet lamp for polymerization for 8 hours to obtain a dynamic soft material, namely the seed 1.
Example 3
The preferred embodiment of the invention provides a preparation method of a dynamic soft material capable of continuously growing, which comprises the following specific steps:
and (3) selecting a first type of monomer: acrylic acid; and (3) selecting a second type of monomer: dimethylaminoethyl methacrylate; and (3) selecting a photoinitiator: alpha-ketoglutaric acid.
5g of acrylic acid and 20mg of alpha-ketoglutaric acid are added into 5g of water, mixed evenly and polymerized for 8 hours under an ultraviolet lamp, thus obtaining the polymer.
10g of dimethylaminoethyl methacrylate and 18mg of alpha-ketoglutaric acid are taken, added into 10g of water, mixed evenly, added into the prepared polymer 1, and subjected to standing overnight and then placed under an ultraviolet lamp for polymerization for 8 hours, thus obtaining the dynamic soft material, namely the seed 1.
Example 4:
taking the seed material obtained in the example 1, adding 5g of acrylic acid and 20mg of alpha-ketoglutaric acid into 5g of water, uniformly mixing, adding the seed material, swelling and balancing for 12 hours, and polymerizing for 8 hours under an ultraviolet lamp to obtain the growing soft material 2.
Taking 5g of dimethylaminoethyl methacrylate and 9mg of alpha-ketoglutaric acid, adding into 5g of water, uniformly mixing, adding the mixed solution into the prepared growing soft material 2, standing overnight, and then placing under an ultraviolet lamp for polymerization for 8 hours to obtain the growing soft material 3.
Example 5:
taking the growing material 3 obtained in the example 4, adding 5g of acrylic acid and 20mg of alpha-ketoglutaric acid into 5g of water, uniformly mixing, adding seed materials, swelling and balancing for 12 hours, and polymerizing for 8 hours under an ultraviolet lamp to obtain the growing soft material 4.
Taking 5g of dimethylaminoethyl methacrylate and 9mg of alpha-ketoglutaric acid, adding into 5g of water, uniformly mixing, adding the mixed solution into the prepared grown soft material 4, standing overnight, and then placing under an ultraviolet lamp for polymerization for 8 hours to obtain the grown soft material 5.
And repeating the growth process in sequence to obtain the grown soft materials 6, 7,8 and 9. The graph of the prepared grown soft material is shown in fig. 4, and the corresponding mechanical properties are shown in fig. 5.
The figure 1 in fig. 4 corresponds to the seed material 5, the figure 2 corresponds to the grown soft material 3, and the figure 3 corresponds to the grown soft material 5. Fig. 5 shows the breaking strength and modulus of different growing soft materials, wherein the broken strength is shown by the dark line.
Example 6:
the acrylic mixed solution containing the initiator is sucked by a needle tube and injected into the seed material obtained in the example 1, the mixture is stood overnight after the injection is completed, and is polymerized for 8 hours under an ultraviolet lamp after the standing overnight, so that the soft material growing in a fixed area can be obtained, the prepared injection growth soft material physical diagram is shown in figure 6,
example 7:
the preferred embodiment of the invention provides performance adjustment of a continuously growing dynamic soft material, comprising the following specific steps:
taking the growth material 1 obtained in example 1, 5g of methyl olefine acid and 18mg of alpha-ketoglutaric acid are added into 5g of water to be uniformly mixed, and then the seed material is added to be swelled and balanced for 12 hours. Polymerizing for 8h under ultraviolet lamp to obtain soft material 1-1.
Taking 5g of dimethylaminoethyl methacrylate and 9mg of alpha-ketoglutaric acid, adding into 5g of water, uniformly mixing, adding the mixed solution into the prepared soft material 1-1 for growing, standing overnight, and then placing under an ultraviolet lamp for polymerization for 8 hours to obtain the soft material 1-2 for growing. The mechanical properties of the prepared grown soft material are shown in fig. 7.
As shown in fig. 7, since hard methacrylic acid was selected as the first type monomer, the breaking strength and modulus of the soft material after growth (sample 1-2) were significantly higher than those of the seed material (sample 1-1), and the soft material after further growth with the second monomer (sample 1-3) had a corresponding mechanical strength significantly reduced but still higher than that of the seed material.
Example 8:
the preferred embodiment of the invention provides for the growth of a continuously growing dynamic soft material, comprising the following steps:
cutting the seed material obtained in example 1 into round pieces, placing the round pieces in a round die with fixed upper and lower intervals, then adding an acrylic acid mixed solution containing an initiator, standing overnight, and placing under an ultraviolet lamp for polymerization for 8 hours to obtain a soft material which grows transversely.
Placing the obtained growth material in a fixed square die with fixed edges, adding a mixed solution of dimethylaminoethyl methacrylate containing an initiator, standing overnight, and polymerizing under an ultraviolet lamp for 8h to obtain a growth soft material limited in the transverse direction and the longitudinal direction. A diagram of the prepared dynamic soft material with limited growth is shown in FIG. 8.
The present invention is not limited to the above-described preferred embodiments, and any person who can obtain other various products under the teaching of the present invention, however, any change in shape or structure of the product is within the scope of the present invention, and all the products having the same or similar technical solutions as the present application are included.
Claims (8)
1. A method for preparing a dynamic soft material capable of continuously growing, which is characterized by comprising the following steps:
s1, placing a first type of monomer into an aqueous solution, adding an initiator, and polymerizing to obtain a polymer;
s2: placing a second type of monomer into an aqueous solution, adding an initiator with corresponding concentration to obtain a monomer solution, adding the monomer solution into the polymer prepared in the step S1, and obtaining a seed material in a polymerization mode, wherein the first type of monomer and the second type of monomer are polymerized into a supermolecular structure;
s3, subjecting the seed material prepared in the step S2 to at least one growth cycle to obtain a growth material, wherein the process of each growth cycle is as follows: adding a first type monomer containing an initiator into the seed material or the growth material obtained in the previous step, swelling the first type monomer, and polymerizing to obtain a growth material after growth, wherein the addition amount of the first type monomer is equal to the mass of the first type monomer in the step S1, continuing adding a corresponding second type monomer containing the initiator, swelling the second type monomer, and polymerizing to obtain a growth material serving as a generation material, wherein the addition amount of the second type monomer is equal to the mass of the second type monomer in the step S2;
the first type of monomer is selected from one or a combination of the following molecular structures;
the second type of monomer is selected from one or a combination of the following molecular structures:
wherein:
；
when the first type monomer is of an acid structure, the second type monomer is of a basic structure; when the first type of monomer is in an ionic structure, the second type of monomer is in a quaternary ammonium salt structure.
2. The method for preparing a continuously growing dynamic soft material according to claim 1, wherein the functional group of the first type of monomer is one or more of carboxyl group, sulfonic group, sodium carboxylate and sodium sulfonate.
3. The method for preparing a continuously growing soft material according to claim 1, wherein the functional group of the second type of monomer is one or more of amino group, tertiary ammonia, quaternary ammonium salt.
4. The method for preparing a continuously growing dynamic soft material according to claim 1, wherein in the growing process, the mass ratio of the first type monomer to the second type monomer is 1:0.1 to 10.
5. The method of producing a continuously growing dynamically soft material according to claim 1, characterized in that in step S3 a monomer solution containing an initiator is injected into the seed material or the growing material spot area obtained in the previous step.
6. A continuously growing dynamic soft material, characterized in that it is prepared by the method for preparing a continuously growing dynamic soft material according to any one of claims 1 to 5.
7. The continuously growing dynamic soft material of claim 6, wherein the dynamic soft material incorporates different substrates.
8. Use of a continuously grown dynamic soft material according to claim 6 for the preparation of functional materials.
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