CN108192020B - Preparation method of intelligent zwitterionic polymer material - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
A preparation method of an intelligent zwitterionic polymer material comprises the following steps: (1) dissolving a zwitterion monomer, a functional monomer, a reinforcing agent, a cross-linking agent and a catalyst in water, and then dropwise adding an accelerator at the temperature of 20-40 ℃ for reaction; (2) and heating to 40-55 ℃, continuing to react until the system does not flow obviously, and gradually heating and drying to obtain the intelligent zwitterionic polymer material. The method takes the betaine monomer as the main raw material to prepare the intelligent high polymer material with the functions of shape memory, self-repairing, pollution resistance and the like.
Description
Technical Field
The invention relates to a preparation method of an intelligent zwitterionic polymer material, in particular to a preparation method of a high polymer material with the functions of shape memory, self-repairing, pollution resistance and the like, and belongs to the technical fields of bionic materials, biomedicine and drug release.
Background
At present, more and more artificial materials are widely applied in the fields of biological detection, biochemical equipment, bioengineering materials, human body implantation materials and the like. Among the biological materials, the high molecular material has the advantages of wide raw materials, flexible molecular design, diversified performances, easy processing and the like. Among them, the intelligent polymer material is one of the most rapidly developed materials. The smart material is a stimulus-responsive material that strongly responds to a change in the surrounding environment, such as a change in shape, surface characteristics or solubility, complex molecular self-assembly, and phase transition from a solution to a gel.
The stimulus-responsive polymer is a macromolecular system with intelligent behavior, and after receiving a stimulus signal of an external environment, the stimulus-responsive polymer has certain physical properties or chemical properties such as molecular configuration, solubility, chemical bond formation and breakage and the like to embody specific intelligent behavior. The external environment stimulation mode is mainly divided into two types of chemical stimulation and physical stimulation. The chemical stimulation mode can change the molecular chain structure of the polymer, change the chemical factors of the interaction between polymer molecular chains or between the polymer molecular chains and a solvent, such as pH value, ionic strength, redox and the like. The physical stimulus means factors that cause interaction between molecules and various energy changes, such as temperature, light, electric field, mechanical stress, and the like. These external stimuli cause reversible or irreversible changes in the polymer structure, which cause the transformation of the bulk or liquid phase behavior of the system. Therefore, the stimulus response polymer has wide application prospect in the fields of nano material science, life science and clinical medicine.
Among stimuli-responsive polymers, shape memory polymers, self-healing polymers, and the like are important intelligent materials. Typical Shape Memory Polymers (SMPs) are capable of "remembering" a macroscopic (permanent) shape, setting to a temporary and static shape under ambient conditions of temperature and pressure, and returning to the initial state under environmental control of temperature, light, water, etc. The SMP with the properties of two different shapes under different conditions gives the material application value in the fields of sensors, intelligent equipment and the like. The self-repairing high molecular material (SHP) is inspired by nature, simulates the healing of organism injury, and enables micro cracks which are difficult to be found by naked eyes in the processing or using process of the material to automatically heal the micro injury of the material through a substance supply or energy supply mechanism. The characteristic prolongs the service life of the material and reduces the use cost. Therefore, shape memory and self-repair are both "intelligent" and "desirable" features of materials, which has led more and more researchers to construct research with self-repair and shape memory properties.
The research trend of intelligent materials at home and abroad is to apply intelligent polymers to the field of biomedicine. However, most shape memory polymers are not biocompatible and, for example, shape memory polyurethanes, when implanted in humans, cause inflammatory reactions in the body. Zwitterionic polymers have attracted considerable attention as a special class of polymeric materials due to their excellent biocompatibility.
Disclosure of Invention
Therefore, the invention aims to provide a preparation method of an intelligent zwitterionic polymer material, which takes a betaine monomer as a main raw material to prepare an intelligent high polymer material with the functions of shape memory, self-repairing, pollution resistance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an intelligent zwitterionic polymer material comprises the following steps:
(1) dissolving a zwitterion monomer, a functional monomer, a reinforcing agent, a cross-linking agent and a catalyst in water, and then dropwise adding an accelerator at the temperature of 20-40 ℃ for reaction;
(2) heating to 40-50 ℃ and continuing the reaction until the system does not flow obviously; the temperature rise in the step can improve the monomer conversion rate and increase the molecular weight and strength of the material;
(3) and further heating and drying to obtain the intelligent zwitterionic polymer material.
The method of the invention takes the zwitterionic monomer, such as betaine type zwitterionic monomer, as the main raw material, and the polymer forms a dual-network structure through the free radical copolymerization reaction to prepare the intelligent zwitterionic polymer material, and the preparation process has the advantages of mild conditions, simple process, stable operation conditions and the like.
A zwitterionic polymer (also known as amphoteric betaine polymer or amphoteric polyelectrolyte) is a polymer having both anionic and cationic groups, and has the same number of positive and negative charges on its side chain and is electrically neutral. The solvation effect of the positive and negative ion groups is strong, and a hydration layer can be formed on the surface of the polymer through the oxygen bond effect, so that non-protein adsorption and the like can be effectively resisted. Therefore, the zwitterionic polymer has important biological characteristics and has wide application prospects in the fields of nano material science, life science and clinical medicine.
The intelligent zwitterionic polymer material prepared by the invention not only has good shape memory and self-repairing functions, but also combines the excellent biological characteristics and non-protein adsorption resistance of the zwitterionic polymer, so that the intelligent zwitterionic polymer material has a certain application prospect in the fields of bionics materials, medicine and the like, and the intelligent characteristic of a high polymer material is fully reflected.
Preferably, in the step (1), the addition amount of each component in parts by weight is 18-35 parts of zwitterionic monomer, 2-8 parts of functional monomer, 40-75 parts of water, 0.1-2 parts of cross-linking agent, 0.2-2.5 parts of catalyst, 0.4-4 parts of accelerator, 1-5 parts of reinforcing agent, preferably 18-35 parts of zwitterionic monomer, 2-8 parts of functional monomer, 55-75 parts of water, 0.1-2 parts of cross-linking agent, 0.2-2.5 parts of catalyst, 1-4 parts of accelerator and 1.5-4 parts of reinforcing agent.
Preferably, the water is deionized water.
Preferably, the zwitterionic monomer, the functional monomer, the reinforcing agent, the cross-linking agent and the catalyst are dissolved in water and then stirred for 2-10 hours to be completely uniform.
Preferably, the zwitterionic monomer, functional monomer, reinforcing agent, crosslinking agent and catalyst are deoxygenated after being dissolved in water, such as by evacuating and filling with at least one of nitrogen or an inert gas and repeating the process several times to remove the oxygen.
Preferably, the zwitterionic monomer is a combination of 1 or more than 2 of carboxylic acid betaine methyl methacrylate, methacryloyl ethyl sulfobetaine or methacryloyl oxyethyl phosphorylcholine.
Preferably, the functional monomer is 1 or more than 2 of hydroxyethyl methacrylate, 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 3, 4-dihydroxyphenyl acrylic acid or hydroxypropyl methacrylate.
Preferably, the crosslinking agent is 1 or more than 2 of phenylboronic acid, borax, N-methylene bisacrylamide or boric acid, preferably phenylboronic acid and/or boric acid. The borate crosslinking system is introduced into the polymer system, so that the network material has a reversible conversion function, and the application function in the fields of performance regulation and control release is enhanced.
Preferably, the catalyst is potassium sulfate, hydrogen peroxide, cumene hydroperoxide, sodium chlorate or ammonium persulfate.
Preferably, the accelerator is sodium thiosulfate, ferrous sulfate, dodecanethiol, or tetramethylethylenediamine.
Preferably, the reinforcing agent is polyvinyl alcohol, polyethylene oxide or polyacrylic acid.
Preferably, the time for dropping the accelerator for reaction is 0.5-1.5 hours. The reaction is preferably carried out with stirring.
Preferably, the reaction mixture after the reaction of step (1) is completed is transferred to a rectangular parallelepiped polytetrafluoroethylene mold.
Preferably, the length and width of the rectangular parallelepiped polytetrafluoroethylene mold is 70mm 15mm 10 mm.
Preferably, the temperature in the step (2) is raised to 40-50 ℃ and the reaction is continued for 20-24 hours.
Preferably, the heating and drying in the step (3) is performed by heating to 50-65 ℃, drying for 8-10 hours, and then heating to 65-90 ℃ and drying for 20-24 hours. After the drying is finished, the temperature is reduced, and the obtained polymer sample is taken out from the mold. In order to evaporate the water, a stage heating and drying mode is adopted to prevent bubbles generated in the water evaporation process from influencing the performance of the material, and the heating mode can reduce the generation of the bubbles to the maximum extent so as to ensure that the performance of the prepared material is optimal.
Preferably, the preparation method of the invention comprises the following steps:
dissolving the measured zwitterion monomer, functional monomer, reinforcing agent, cross-linking agent and catalyst in a closed reactor, dissolving the mixture in a certain amount of deionized water, stirring for 2-10 hours to ensure that the mixture is completely uniform, vacuumizing, filling nitrogen and repeatedly deoxidizing for many times; dropwise adding a quantitative accelerator at the controlled temperature of 20-40 ℃, reacting for 0.5-1.5 hours under stirring, pouring into a polytetrafluoroethylene mold with the size of 70mm x 15mm x 10mm, heating to 40-50 ℃, and standing for reacting for 20-24 hours; and when the reaction system does not flow obviously, gradually heating to 50-65 ℃, drying for 8-10 hours, heating to 65-90 ℃, drying for 20-24 hours, and cooling and taking out the obtained zwitterionic polymer sample from the mold.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a preparation method of an intelligent polymer material with a zwitterionic network structure, the material has special properties such as shape memory and self-repairing, and the introduction of the zwitterionic polymer enables the material to have excellent biological characteristics and anti-pollution functions, and the material has a certain application prospect in the fields of bionics materials, medicine and the like.
2. According to the invention, a borate crosslinking system is introduced into a polymer system, so that the network material has a reversible conversion function, and the application function in the fields of performance regulation and control release is enhanced.
3. The preparation method provided by the invention is simple, mild in reaction condition, stable in process operation, strong in implementability, low in comprehensive cost and remarkable in economic benefit.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Selecting 80 ℃ to test the shape fixation rate and the recovery rate; measuring the self-repairing efficiency of the fractured polymer material after the fractured polymer material is self-repaired for 24 hours by using a universal testing machine; and testing the hemoglobin adsorption resistance of the material by an ultraviolet spectrophotometer.
Example 1
A preparation method of an intelligent zwitterionic polymer material comprises the following steps:
(1) preparation of functional monomer: 13 parts of glycidyl methacrylate, 87 parts of deionized water and 1 part of hydroquinone were charged into a reactor with a condenser tube. Heating to 85 ℃, stirring the initial emulsion for 11 hours to form a homogeneous aqueous solution, rotationally evaporating water in the mixed solution, removing hydroquinone by using neutral aluminum oxide to obtain a light yellow liquid as a functional monomer: 2-methyl-2-propenoic acid 2, 3-dihydroxypropyl ester.
(2) Preparation of smart zwitterionic polymers: 20 parts of carboxylic betaine methyl methacrylate, 6.5 parts of the self-made functional monomer, 64 parts of deionized water, 2 parts of boric acid, 3 parts of polyvinyl alcohol and 1.5 parts of ammonium persulfate are weighed and added into a reactor, stirred for about 2 hours to be dissolved and uniformly mixed, vacuumized and filled with nitrogen, and oxygen is fully removed repeatedly. 3 parts of tetramethylethylenediamine is dripped at the temperature of 30 ℃, the mixture is stirred to react for 1 hour, then the mixture is poured into a polytetrafluoroethylene mold, and the temperature is raised to 40 ℃ for static reaction for 24 hours. When the reaction system does not flow obviously, the temperature is raised to 55 ℃ for drying for 10h, then the temperature is raised to 85 ℃ for drying for 24h, and the polymer sample is taken out from the die after the temperature is reduced.
The determination shows that the shape fixing rate is 96 percent, the shape recovery rate is 91 percent, the self-repairing efficiency is 81 percent after 24 hours, and the serum protein anti-adsorption rate is 95 percent under the condition of 80 ℃.
Example 2
A preparation method of an intelligent zwitterionic polymer material comprises the following steps:
(1) the functional monomers were prepared as in example 1.
(2) Preparation of smart zwitterionic polymers: 22 parts of methacryloyl ethyl sulfobetaine, 3 parts of the self-made functional monomer, 65 parts of deionized water, 3 parts of polyacrylic acid, 2 parts of boric acid and 2 parts of ammonium persulfate are added into a three-neck flask and stirred for 3 hours to be completely dissolved, and the three-neck flask is vacuumized, filled with nitrogen and repeatedly and fully deoxygenated. 3 parts of tetramethylethylenediamine is dripped at the temperature of 30 ℃, and the mixture is stirred to react for 1 hour and then poured into a polytetrafluoroethylene mold. Then the temperature is raised to 40 ℃ and the reaction is carried out for 22 hours. And when the reaction system is in a gel state, heating to 55 ℃ for drying for 10 hours, heating to 85 ℃ for drying for 24 hours, and taking out the polymer sample from the mold after cooling.
The determination shows that the shape fixation rate is 95 percent, the shape recovery rate is 92 percent, the self-repairing efficiency is 82 percent after 24 hours, and the serum protein anti-adsorption rate is 96 percent under the condition of 80 ℃.
Example 3
A preparation method of an intelligent zwitterionic polymer material comprises the following steps:
1.5 parts of N, N-methylene bisacrylamide and 67 parts of deionized water are added into a three-neck flask and stirred for 1-2 hours. After the materials are completely dissolved, 20 parts of carboxylic betaine methyl methacrylate, 5 parts of hydroxyethyl methacrylate, 2.5 parts of polyethylene oxide and 2 parts of ammonium persulfate are metered into a three-neck flask and are continuously stirred for 1 hour to be completely dissolved, and the three-neck flask is vacuumized, filled with nitrogen and repeatedly and fully deoxygenated. Controlling the temperature to be 35 ℃, adding 2 parts of sodium thiosulfate, reacting for 1 hour under stirring, pouring into a polytetrafluoroethylene mold, heating to 45 ℃, and standing for reacting for 24 hours. When the reaction system does not flow obviously, the temperature is raised to 60 ℃ for drying for 9 hours, then the temperature is raised to 90 ℃ for drying for 24 hours, and a polymer sample is taken out after the temperature is reduced.
The determination shows that the shape fixing rate is 90 percent, the shape recovery rate is 90 percent, the self-repairing efficiency is 80 percent after 24 hours, and the serum protein anti-adsorption rate is 96 percent under the condition of 80 ℃.
Example 4
A preparation method of an intelligent zwitterionic polymer material comprises the following steps:
25 parts of methacryloyloxyethyl phosphorylcholine, 4 parts of hydroxypropyl methacrylate, 60 parts of deionized water, 2 parts of phenylboronic acid, 3 parts of polyvinyl alcohol and 2 parts of potassium persulfate are added into a three-neck flask and stirred for about 3 hours to be completely dissolved and uniformly mixed, and the three-neck flask is vacuumized, filled with nitrogen and repeatedly and fully deoxygenated. 4 parts of tetramethylethylenediamine is dropwise added at the temperature of 33 ℃, the mixture is stirred and reacts for 0.5 hour, then the mixture is poured into a polytetrafluoroethylene mold, and the temperature is raised to 40 ℃ for static reaction for 24 hours. When the reaction system does not flow obviously, the temperature is raised to 55 ℃ for drying for 10 hours, then the temperature is raised to 85 ℃ for drying for 24 hours, and a polymer sample is taken out after the temperature is reduced.
The determination shows that the shape fixing rate is 91 percent, the shape recovery rate is 92 percent, the 24-hour self-repairing efficiency is 80 percent, and the serum protein anti-adsorption rate is 94 percent under the condition of 80 ℃.
The material prepared by the invention has high shape fixation rate and shape recovery rate, so that the material is more applied to the fields of medical bionic materials such as brackets, bionic tapes and the like. The shape of the intelligent material can change along with external stimulation conditions; the self-repairing performance enables cracks and micro-damage generated when the material is applied to be automatically healed under the condition of not adding a repairing agent, and the service life is prolonged; the prepared zwitterionic material has hydration effect, can eliminate negative effects, and is outstanding as an anti-fouling material.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A preparation method of an intelligent zwitterionic polymer material comprises the following steps:
(1) dissolving a zwitterion monomer, a functional monomer, a reinforcing agent, a cross-linking agent and a catalyst in water, and then dropwise adding an accelerator at the temperature of 20-40 ℃ for reaction; the zwitterionic monomer is a combination of 1 or more than 2 of carboxylic acid betaine methyl methacrylate, methacryloyl ethyl sulfobetaine or methacryloyl oxyethyl phosphorylcholine; the functional monomer is the combination of 1 or more than 2 of hydroxyethyl methacrylate, 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester, 3, 4-dihydroxyphenyl acrylic acid or hydroxypropyl methacrylate; the cross-linking agent is 1 or more than 2 of phenylboronic acid, borax, N-methylene bisacrylamide or boric acid; the catalyst is potassium persulfate, hydrogen peroxide, cumene hydroperoxide or ammonium persulfate;
the accelerator is sodium thiosulfate, ferrous sulfate, dodecyl mercaptan or tetramethyl ethylene diamine;
the reinforcing agent is polyvinyl alcohol, polyoxyethylene or polyacrylic acid;
(2) heating to 40-50 ℃ and continuing the reaction until the system does not flow obviously;
(3) and further heating and drying to obtain the intelligent zwitterionic polymer material.
2. The preparation method according to claim 1, wherein the components in the step (1) are added in an amount of 18 to 35 parts by weight of the zwitterionic monomer, 2 to 8 parts by weight of the functional monomer, 40 to 75 parts by weight of water, 0.1 to 2 parts by weight of the crosslinking agent, 0.2 to 2.5 parts by weight of the catalyst, 0.4 to 4 parts by weight of the accelerator and 1 to 5 parts by weight of the reinforcing agent.
3. The method according to claim 1, wherein the crosslinking agent is phenylboronic acid and/or boric acid.
4. The preparation method according to claim 1, wherein in the step (1), the zwitterionic monomer, the functional monomer, the reinforcing agent, the cross-linking agent and the catalyst are dissolved in water and then stirred for 2-10 hours;
the amphoteric ion monomer, the functional monomer, the reinforcing agent, the cross-linking agent and the catalyst are dissolved in water to remove oxygen.
5. The preparation method according to claim 1, wherein the time for dropping the accelerator in the step (1) for the reaction is 0.5 to 1.5 hours;
transferring a reaction mixture into a cuboid polytetrafluoroethylene mold after the reaction in the step (1) is finished;
the length, width and height of the cuboid polytetrafluoroethylene mould are 70mm 15mm 10 mm.
6. The method according to claim 1, wherein the reaction is continued for 20 to 24 hours while the temperature in step (2) is increased to 40 to 50 ℃.
7. The preparation method according to claim 1, wherein the heating and drying in step (3) is performed by heating to 50-65 ℃, drying for 8-10 hours, and then heating to 65-90 ℃ and drying for 20-24 hours.
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| CN111714410B (en) * | 2019-12-27 | 2024-01-05 | 杭州奥菲生物科技有限公司 | Oral care composition of non-phosphoric acid system and preparation method thereof |
| CN113045698B (en) * | 2019-12-27 | 2024-02-06 | 黄石市森尔新型材料有限公司 | Zwitterionic polymer and preparation method and application thereof |
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| CN113073477B (en) * | 2021-03-22 | 2022-03-11 | 四川大学 | Super-hydrophilic anti-fouling cotton fabric for oil-water separation and zwitterionic hydrogel for cotton fabric |
| CN113930000A (en) * | 2021-10-20 | 2022-01-14 | 台湾塑胶工业股份有限公司 | Polyethylene colloidal particles for resisting adhesion of biological molecules and preparation method thereof |
| CN114316144B (en) * | 2022-01-10 | 2023-04-25 | 浙江大学 | High-strength self-restorable multifunctional conductive hydrogel with temperature/pH dual response and preparation method and application thereof |
| CN114592350B (en) * | 2022-03-07 | 2024-05-14 | 盐城工业职业技术学院 | Knitted fabric with dual functions of warming, ventilation and air purification and preparation method thereof |
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