CN113336895B - Supported polymer and supported hydrogel - Google Patents

Supported polymer and supported hydrogel Download PDF

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CN113336895B
CN113336895B CN202110592966.9A CN202110592966A CN113336895B CN 113336895 B CN113336895 B CN 113336895B CN 202110592966 A CN202110592966 A CN 202110592966A CN 113336895 B CN113336895 B CN 113336895B
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supported
electrolyte
hydrogel
electrolyte monomer
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CN113336895A (en
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郭宏磊
汤卓夫
黄广
孟国哲
雷冰
冯志远
郭辉
梁涣森
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide

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  • Polymers & Plastics (AREA)
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Abstract

The invention relates to the technical field of polymers, in particular to a supported polymer and a supported hydrogel. The invention discloses a supported polymer, which consists of a polymer and polyvalent anions supported on the polymer; the polymer comprises at least one electrolyte unit; the electrolyte unit has a structure shown in a formula (I) or a formula (II). Positively charged R in the supported polymer 1 The group can be used as a loading point of anions, especially acid radical ions, and the anions are loaded in the polymer by utilizing electrostatic action. Under certain external stimuli (such as polyvalent metal ions), the polymer can release anions and can also be loaded again based on the conversion between different balances.

Description

Supported polymer and supported hydrogel
Technical Field
The invention relates to the technical field of polymers, in particular to a supported polymer and a supported hydrogel.
Background
The traditional water treatment method is mainly to directly add a water treatment agent into sewage, but the dosage of the water treatment agent cannot be accurately controlled, which inevitably leads to waste. In the metal corrosion inhibition application, the traditional method for directly adding the corrosion inhibitor is uneconomical, and the corrosion inhibitor is easy to fail, so that the water treatment agent/corrosion inhibitor is loaded in the hydrogel, and the utilization rate of the water treatment agent/corrosion inhibitor can be improved. There are many applications of hydrogels/polymers in the field of loading and release of small molecules today, such as n.pirhady Tavandashti et al, which use polyaniline loaded 2-mercaptobenzotriazole corrosion inhibitors with hollow nanostructures, which are then doped into epoxy resin coatings, where primary amines release the corrosion inhibitors when stimulated by external pH. However, during loading and release of the corrosion inhibitor, when the pH of the environment changes, the release does not stop after the start, and thus the amount cannot be accurately controlled. (Corrosion Science, volume 112,November 2016,Pages138-149). While more research is currently being conducted on drug loading using block-type polymers, di-or multiblocks, with different blocks achieving encapsulation and loading functions, respectively, such as Ganivada M N, jommaee N et al using a primary amine-type block copolymer, encapsulating the drug in microcapsules with the self-assembly of hydrophobic segments and the positive charge generated by partial ionization of primary amine, also pH stimulus-responsive release (ACS Biomaterials Science & Engineering,2017,3 (6): 903-908, carbohydrate polymers,2018, 198:486-494). However, the preparation method of the block polymer is complicated, the reaction condition is harsh, and the preparation method is accompanied by higher preparation cost, so that the preparation method is not economical enough.
Disclosure of Invention
In view of this, the present invention provides a supported polymer containing positively charged groups, which can support a functional substance containing anions, and which can realize intelligent release of the functional substance containing anions by a certain external stimulus.
The specific technical scheme is as follows:
the present invention provides a polymer comprising: a polymer and an anion supported on the polymer;
the polymer contains at least one electrolyte unit;
the electrolyte unit has a structure shown in a formula (I) or a formula (II);
wherein R is 1 Quaternary ammonium ion, quaternary phosphonium ion, sulfonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, or zwitterionic;
R 2 is phenyl, C0-C20 alkyl or C0-C20 alkoxy;
the compound of the structure shown in the formula (I) does not contain R 3 Or R is 3 Selected from amide groups and ester groups;
R 4 selected from hydrogen or methyl;
R 5 、R 6 each independently selected from methyl, ethyl or phenyl.
In the present invention, the polymer is loaded with anions by electrostatic action. The polymer provided by the invention is formed by copolymerizing electrolyte monomers. Positively charged R in the polymers provided by the invention 1 The group, which can be the loading point for anions, especially acid ions, electrostatically loads the anions into the polymeric material. Under certain external stimuli (such as cation concentration), the polymer can release anions and can also be loaded again based on the conversion between different balances.
In the present invention, the polymer further comprises: at least one non-electrolyte cell;
the non-electrolytic unit includes a non-electrolyte monomer copolymerized with an electrolyte monomer of the electrolyte unit, the non-electrolyte monomer having the following structure:
the electrolyte groups in the polymer provided by the invention can be severely expanded in water and have poor mechanical properties due to the internal electrostatic repulsion effect, and the mechanical properties of the polymer can be effectively enhanced by introducing the non-electrolyte monomer into the polymer.
In the present invention, the molar ratio of the electrolyte monomer to the non-electrolyte monomer is (10:1) - (1:99), preferably 1: (5 to 20), more preferably 1: 5. 1:10 or 1:20.
in the invention, the general formula of the quaternary ammonium ion is as follows: r is R 10 R 11 R 12 N + The general formula of the quaternary phosphine ion is R 10 R 11 R 12 P + The sulfonium ion has a general formula of R 10 R 11 S + 。
The zwitterionic groups are:
wherein a is more than or equal to 1 and less than or equal to 10, preferably a is more than or equal to 2 and less than or equal to 4, b is more than or equal to 1 and less than or equal to 10, preferably b is more than or equal to 2 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 10, preferably c is more than or equal to 2 and less than or equal to 4, d is more than or equal to 1 and less than or equal to 10, and preferably d is more than or equal to 2 and less than or equal to 4.
In the invention, the imidazolium ions are:
the pyridinium ions are:
the piperidinium ions are:
the pyrrolidinium ions are:
wherein, represents a group and R 2 Is connected to the connecting point of (c).
The electrolyte monomer preferably includes:
one or two or more of them.
In the present invention, the non-electrolyte monomer preferably includes:
one or two or more of them.
In the above structure, R 2 Phenyl, C0-C20 alkyl or C0-C20 alkoxy, preferably 1-10, more preferably 1-4.
R 3 Selected from amide groups or ester groups.
R 4 Selected from hydrogen or methyl.
R 5 、R 6 Each independently selected from methyl, ethyl or phenyl.
R 7 Selected from hydrogen or methyl.
R 8 Is an amide group or an ester group.
R 9 The alkyl group is preferably a C1 to C20, unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms, more preferably a C1 to C4 unsubstituted straight-chain alkyl group.
R 10 、R 11 、R 12 Each independently selected from methyl, ethyl or phenyl.
R 13 、R 14 Is hydrogen, C1-C10 alkyl or C1-C10 alkoxy, preferably C1-C10 alkyl, more preferably C1-C4 alkyl, more preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl or tert-butylButyl.
R 15 Is amino, cyano, hydroxy, amide bond, ureido,
In the present invention, the electrolyte monomer is preferably acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, allyl trimethyl phosphorus chloride or 1-allyl-tetrahydrothiophene bromide. The invention also provides a supported hydrogel which is obtained by crosslinking a supported polymer.
It should be noted that, the charge in the electrolyte gel can load multivalent anions, however, the traditional electrolyte gel has great volume change before and after loading and even can be damaged in the process, so that the polymer containing the non-electrolyte monomer can not be practically applied, the swelling of the polymer is inhibited to a certain extent, the mechanical property of the polymer is enhanced, and the inhibition degree depends on the strength and the quantity of physical actions in the gel. The enhancement of mechanical properties ensures the integrity of the polymer in the conversion process and ensures the possibility of recycling the polymer.
In the invention, the release of anions in the supported hydrogel is realized based on the intensity of the ion stimulation of the external environment, which is different from the diffusion release of pH response, and the release can be stopped when the stimulation is below a critical value, so that the intelligent release is realized. For example: anions loaded on the polymer are released from the carrier when encountering cations bound with the anions, the anions can be quantitatively released according to the concentration of the cations, the anions are stopped in time, and the anions are released again when concentration stimulus is generated again. The supported polymer realizes intelligent release of active substances with different functions according to different functions of the supported anions.
In the invention, the charged hydrogel is used as a carrier, positive charges are utilized to adsorb anions, and the mechanical properties of the polymer are further improved through regulating and controlling the number and the distance of the charges, so that the polymer has more excellent mechanical properties than the conventional electrolyte hydrogel.
In the invention, the polyvalent anions comprise one or more than two of chromate, molybdate, tungstate, vanadate, borate, hexametaphosphate, selenite, phytate, aminotrimethylene phosphonate, ethylenediamine tetraacetate, ethylenediamine tetramethylene phosphonate, hydroxyisomethylene diphosphonate, tripolyphosphate, citrate, maleate and polyacrylate, preferably borate, selenite, hexametaphosphate, phytate, ethylenediamine tetramethylene phosphonate, hydroxyisomethylene diphosphonate, tripolyphosphate, citrate and polyacrylate; more preferably hexametaphosphate, tripolyphosphate, ethylenediamine tetraacetate. Preferably hexametaphosphate, citrate, phytate.
The invention also provides a first preparation method of the supported hydrogel, which comprises the following steps:
step 1: mixing an electrolyte monomer or a precursor of the electrolyte monomer, an initiator, inorganic salt, a cross-linking agent and an organic solvent to obtain a pre-reaction solution;
step 2: and under the initiation condition, the pre-reaction solution is subjected to polymerization reaction to obtain the polymer.
Step 3: the polymer is transferred to be mixed with an anionic salt solution, and the loaded hydrogel is obtained after filtration.
In the present invention, if the polymer in the loaded hydrogel contains a non-electrolyte monomer, the loaded hydrogel needs to be added with the non-electrolyte monomer in step 1 during the preparation process.
The step 1 of the invention specifically comprises the following steps: dissolving electrolyte monomer or precursor of electrolyte monomer, initiator and cross-linking agent in solvent, mixing, adding inorganic salt and mixing to obtain pre-reaction solution;
or the electrolyte monomer or the precursor of the electrolyte monomer, the non-electrolyte monomer, the initiator and the inorganic salt are dissolved in a solvent together to obtain a pre-reaction solution.
The inorganic salt comprises one or more of sodium chloride, potassium chloride, lithium chloride, sodium nitrate, potassium thiocyanate and sodium thiocyanate;
the initiator is a photoinitiator, a thermal initiator or a redox initiator. The choice of the initiator according to the invention is determined on the basis of the initiation conditions described in step 2, the photoinitiator is used by irradiation with ultraviolet light, the initiator is not required by irradiation with microwaves or gamma rays, and the thermal initiator is used by a heating method. The invention preferably uses ultraviolet light irradiation, and the initiator is preferably a photoinitiator, more preferably alpha-ketoglutarate and azobisisobutyronitrile;
the solvent is an organic solvent and/or water; the organic solvent comprises one or more of methanol, ethanol, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, butanone, cyclohexanone, ethyl formate, tetrahydrofuran, dioxane, acetone, tetrachloroethane, propionitrile, pyridine, cyclohexanol, N-butanol, isopropanol, N-propanol, acetonitrile, dimethylacetamide, acetic acid, ethylene carbonate, malononitrile, ethylene glycol, glycerol and formamide. The solvent is preferably water or a mixed solvent of ethanol and water, and the volume ratio of ethanol to water in the mixed solvent is preferably 1:1.
the crosslinking agent is a multi-olefin compound, preferably a difunctional crosslinking agent, more preferably N, N-methylene bisacrylamide and 1, 4-butanediol diacrylate.
In the step 1 of the present invention, the total molar concentration of the electrolyte monomer or the precursor of the electrolyte monomer and the non-electrolyte monomer in the pre-reaction solution is 0.1 to 5.0mol/L, preferably 1mol/L, 1.5mol/L and 2mol/L;
the ratio of the total moles of the electrolyte monomer or precursor of the electrolyte monomer to the total moles of the non-electrolyte monomer is (1:0) - (1:99), preferably 1: (5 to 20), more preferably 1: 5. 1:10 or 1:20, a step of; the polymers provided by the present invention need not be limited by the proportion and structure of the monomers.
The molar concentration of the initiator is 0.01% -5%, preferably 0.1% of the total molar concentration of the monomers.
The molar concentration of the inorganic salt is 0-20% of the total molar concentration of the monomers, preferably 5%;
the molar concentration of the crosslinking agent is 0% to 4%, preferably 1%, of the total molar concentration of the monomers.
In the step 2, the electrolyte monomer or the precursor of the electrolyte monomer is polymerized by free radicals to obtain a polymer;
the initiation condition of the polymerization reaction is ultraviolet light, microwave, gamma ray irradiation or heating; when the initiation condition is ultraviolet light, the ultraviolet light irradiation time is 6-12h, preferably 8h; when the initiation condition is heating, the heating temperature is 60-100 ℃ and the time is 4-12h, preferably the reaction is carried out at 70 ℃ for 8h; the microwave method and the gamma-ray irradiation method are both initiation methods of polymerization reactions commonly used in the art, and the present invention is not particularly limited.
The polymer provided by the invention is obtained by conventional free radical polymerization, the preparation method is simple, and the raw materials are cheap and easy to obtain.
In the step 3 of the present invention, the concentration of the anion salt-containing solution is 0.0001mol/L to 6mol/L, preferably 0.01 to 2.5mol/L, more preferably 0.05 to 0.4mol/L; the time for soaking the polymer is 12-72 h.
In step 3 of the present invention, before the supported hydrogel is obtained, the method further comprises: soaking the polymer soaked with the anionic salt-containing solution in deionized water, and repeating the soaking for three times to remove redundant anions in the polymer; the time of each soaking is 2-12 hours, preferably 4 hours.
The invention also provides a second preparation method of the supported hydrogel, which comprises the following steps:
step a: mixing electrolyte monomer or precursor of electrolyte monomer, initiator, inorganic salt, cross-linking agent, anion salt and solvent to obtain pre-reaction solution;
step b: and under the initiation condition, the pre-reaction solution is subjected to polymerization reaction to obtain the supported hydrogel.
In the present invention, if the polymer in the loaded hydrogel contains a non-electrolyte monomer, the loaded hydrogel needs to be added with the non-electrolyte monomer in step a during the preparation process.
In the second preparation method of the supported hydrogel of the present invention, in the step a, the concentration of the anionic salt solution is 0.0001mol/L to 2.5mol/L, preferably 0.01 mol/L to 2.5mol/L, more preferably 0.05 mol/L to 0.4mol/L;
the cross-linking agent is a multi-alkene compound, preferably a cross-linking agent with difunctional degree, more preferably N, N-methylene bisacrylamide and 1, 4-butanediol diacrylate;
the molar concentration of the crosslinking agent is 0% -4% of the total molar concentration of the monomers, preferably 1%;
the solvent is an organic solvent and/or water; the organic solvent comprises one or more of methanol, ethanol, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, butanone, cyclohexanone, ethyl formate, tetrahydrofuran, dioxane, acetone, tetrachloroethane, propionitrile, pyridine, cyclohexanol, N-butanol, isopropanol, N-propanol, acetonitrile, dimethylacetamide, acetic acid, ethylene carbonate, malononitrile, ethylene glycol, glycerol and formamide, and the solvent is preferably water or a mixed solvent of ethanol and water.
In the invention, the precursor of the electrolyte monomer is a monomer or a mixture of a plurality of monomers which can participate in polymerization reaction, and the positively charged polyelectrolyte can be obtained through a certain chemical reaction in the later period. The precursor of the electrolyte monomer is preferably a tertiary amine-containing monomer.
In the invention, after anions in the loaded hydrogel prepared by the two methods are released, the loaded hydrogel can be soaked in salt solution containing anions again or salt with acid radical ions is added in the environment to realize reloading.
The supported hydrogel provided by the invention is simple to operate and can be produced in a large scale.
The thickness of the above-mentioned hydrogels and supported hydrogels is not limited, but the thickness of the present invention is preferably 0.5 to 3mm, preferably 1mm or 1.5mm.
The invention also provides application of the supported polymer and the supported hydrogel in adhesives and/or water treatment agents and/or corrosion inhibition rust inhibitors.
The supported hydrogel provided by the invention has good stability in water, can be used as a carrier of a water treatment agent and a corrosion and rust inhibitor, and can realize quantitative release of the water treatment agent/rust inhibitor according to stimulation of external environment ions.
From the above technical scheme, the invention has the following advantages:
the present invention provides a supported polymer composed of a polymer and a polyvalent anion supported on the polymer; the polymer comprises at least one electrolyte unit; the electrolyte unit has a structure shown in a formula (I) or a formula (II). Positively charged R in the supported polymer 1 The group, which can be the loading point for anions, especially acid ions, electrostatically loads the anions into the polymeric material. Under certain external stimuli (such as cation concentration), the polymer can release anions and can also be loaded again based on the conversion between different balances.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a physical diagram of the loaded hydrogel prepared in example 1 of the present invention;
FIG. 2 is a physical diagram of the loaded hydrogel prepared in example 2 of the present invention;
FIG. 3 shows 0.5wt% FeCl without the supported hydrogel treatment in the examples of the present invention 3 A solution;
FIG. 4 shows the process of immersing the supported hydrogel prepared in example 1 of the present invention in 0.5wt% FeCl 3 A physical map of the solution;
FIG. 5 is a graphical representation of the loaded hydrogel prepared in example 2 of the present invention in deionized water;
FIG. 6 shows the process of example 2 of the present inventionThe obtained supported hydrogel is soaked in FeCl with the weight percentage of 0.5 percent 3 A physical map of the solution;
FIG. 7 shows the process of immersing the supported hydrogel prepared in example 3 of the present invention in 0.5wt% FeCl 3 A physical map of the solution;
FIG. 8 shows the process of immersing the supported hydrogel of example 4 in 0.5wt% FeCl 3 A physical map of the solution;
FIG. 9 is a graphical representation of the carbon steel encapsulated with epoxy after one day of immersion in a 1wt% NaCl solution;
FIG. 10 is a physical diagram of the polymer of example 3 after being attached to carbon steel encapsulated with epoxy resin and immersed in a 1wt% NaCl solution for one day;
FIG. 11 is a sample of the hexametaphosphate loaded polymer gel prepared in example 16 immersed in 0.5wt% FeCl 2 Solution and FeCl 3 A physical map of the solution;
FIG. 12 is a Fourier infrared spectrum of a hexametaphosphate loaded polymer gel prepared in example 5.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the embodiments described below are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the supported hydrogel in this example comprises the following specific preparation steps:
step 1: 2.302g of acrylamide (non-electrolyte monomer, NAGA), 0.484g of acryloxyethyl trimethyl ammonium chloride (electrolyte monomer, DAC), 0.031g of N, N-methylenebisacrylamide, 0.0029g of alpha-ketoglutaric acid were dissolved in water/ethanol (1/1) and the volume was set to 10mL to obtain a pre-reaction solution.
Step 2: pouring the prepared clear solution into a glass mold, placing the mold between two ultraviolet lamps, and opening 365nm ultraviolet light to irradiate for 8 hours to obtain hydrogel with the thickness of 1.5mm, wherein the structure is shown as follows.
Step 3: dissolving 12.22g of sodium hexametaphosphate in 80mL of deionized water, fully stirring and dissolving to obtain a colorless transparent solution, fixing the volume to 100mL to obtain a hexametaphosphate solution with the molar concentration of 0.4mol/L, soaking the hydrogel coating prepared in the step 2 in the sodium hexametaphosphate solution for 24 hours, taking out the hydrogel from the solution after the gel is not shrunk any more, then soaking in the deionized water for 4 hours, and repeatedly washing out excessive phosphate ions in the gel three times to obtain the sodium hexametaphosphate-loaded hydrogel with the thickness of 1.5mm.
The loaded hydrogel prepared in step 2 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel. FIG. 1 is a physical diagram of the loaded hydrogel obtained in step 3 of this example; FIG. 3 is a 0.5wt% FeCl without supported hydrogel treatment 3 A solution; FIG. 4 shows the loading of FeCl in the loaded hydrogel obtained in step 3 of this example 3 Physical diagram after solution. As can be seen from FIGS. 1 and 3-4, the hydrogel is transparent and the gel is in FeCl 3 Sodium hexametaphosphate and iron ions are released from the solution to generate precipitation.
Example 2
The preparation of the supported hydrogel in this example comprises the following specific preparation steps:
step 1: 1.531g of methacrylamide (non-electrolyte monomer, mam), 0.540g of diallyldimethylammonium chloride (electrolyte monomer, DMDAAC), 0.031g of N, N-methylenebisacrylamide, 0.250g of sodium hexametaphosphate, 0.016g of 2, 2-azobisisobutyronitrile were dissolved in deionized water and the volume was set to 10mL to obtain a pre-reaction solution.
Step 2: pouring the prepared clear solution into a glass die, heating to 70 ℃ and reacting for 8 hours to obtain the loaded hydrogel with the thickness of 1mm, wherein the structure is shown as follows.
The loaded hydrogel prepared in step 2 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel. FIG. 2 is a physical view of the loaded hydrogel prepared in this example; FIG. 5 is a graphical representation of immersing a loaded hydrogel in deionized water; FIG. 6 shows the loaded hydrogel prepared in the example immersed in FeCl 3 As can be seen from fig. 2, 5 and 6, the hydrogel is white and opaque, the gel does not release corrosion inhibitor in deionized water, and the gel is coated with FeCl 3 Sodium hexametaphosphate and iron ions are released from the solution to generate precipitation.
Example 3
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the non-electrolyte monomer methacrylamide used in step 1 is replaced by: acrylamide, mass 1.271g, concentration in the pre-reaction solution 1.8mol/L.
The loaded hydrogel prepared in step 2 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel. FIG. 7 shows the loaded hydrogel of this example immersed in 0.5wt% FeCl 3 Physical diagram of the solution. FIG. 9 is a graphical representation of corrosion of carbon steel without supported hydrogel protection after one day of immersion in a 1wt% NaCl solution; FIG. 10 is a graph showing the corrosion pattern of carbon steel after the carbon steel is subjected to the attached protection by using the supported hydrogel prepared in example 3, and immersed in NaCl solution for one day. From FIG. 7, it can be seen that the supported hydrogel is in FeCl 3 Sodium hexametaphosphate and iron ions are released from the solution to generate precipitation. From the comparison of fig. 9 and 10, it is understood that the supported hydrogel has a certain corrosion inhibition capability.
Example 4
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the electrolyte monomer used in step 1 is replaced with: methacryloyloxyethyl trimethylammonium chloride; the mass of the reaction mixture was 0.553g, and the concentration of the reaction mixture in the pre-reaction solution was 0.2mol/L.
The loaded hydrogel prepared in step 2 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
FIG. 8 shows the loaded hydrogel of this example immersed in 0.5wt% FeCl 3 Physical diagram of the solution. From the figure, it can be seen that the supported hydrogel is in FeCl 3 Sodium hexametaphosphate and iron ions are released from the solution to generate precipitation.
Example 5
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the electrolyte monomers used in step 1 are: the mass of the acryloxypropyl trimethyl ammonium chloride was 0.552g, and the concentration in the pre-reaction solution was 0.2mol/L. Fig. 12 is a fourier infrared spectrum of a polymer gel loaded with hexametaphosphate. As can be seen from fig. 12, the present example successfully produced a loaded hydrogel.
Example 6
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the electrolyte monomers used in step 1 are: the mass of each methacryloyloxyethyl trimethyl ammonium chloride was 0.591g, and the concentration in the pre-reaction solution was 0.2mol/L.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 7
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the mass of the electrolyte monomer used in the step 1 is as follows: 0.968g, the concentration in the pre-reaction solution being 0.4mol/L; the mass of the non-electrolyte monomer is as follows: 2.050g, the concentration in the pre-reaction solution was 1.6mol/L, respectively.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a hydrogel.
Example 8
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the mass of the electrolyte monomer used in the step 1 is as follows: 1.936g, the concentration in the pre-reaction solution being 0.8mol/L, respectively; the mass of the non-electrolyte monomer is as follows: 1.538g, the concentration in the pre-reaction solution was 1.2mol/L, respectively.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 9
This example is a preparation of a supported hydrogel, which differs from example 1 only in that:
the mass of the electrolyte monomer used in the step 1 is as follows: 2.424g, the concentration in the pre-reaction solution being 1.0mol/L, respectively; the mass of the non-electrolyte monomer is as follows: 1.281g, concentration in the pre-reaction solution, 1.0mol/L, respectively.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 10
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the multivalent anion salts used in step 1 are: sodium pyrophosphate, the mass of which is 0.200g.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 11
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the multivalent anion salts used in step 1 are: sodium tripolyphosphate was 0.200g each by mass.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 12
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the multivalent anion salts used in step 1 are replaced with: sodium citrate, each 0.150g by mass.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 13
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the multivalent anion salts used in step 1 are: pentasodium aminotrimethylene phosphonate, mass 0.300g.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 14
This example is a preparation of a supported hydrogel, which differs from example 2 only in that:
the multivalent anion salts used in step 1 are: sodium ethylenediamine tetraacetate, the mass of which was 0.250g.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 15
This example is a preparation of a supported hydrogel, which differs from example 1 only in that: the electrolyte monomer is acryloyloxyethyl trimethyl ammonium chloride, the mass is 4.484g, and the concentration of the electrolyte monomer is 2mol/L.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
Example 16
The present example is a supported hydrogel, and the preparation method is the same as example 1, except that: the non-electrolyte monomer is N-methacryloylglycine amide, the mass is 2.550g, the concentration is 1.8mol/L, the electrolyte monomer is acryloyloxyethyl trimethyl ammonium chloride, the mass is 0.484g, and the concentration is 0.2mol/L.
The loaded hydrogel prepared in step 3 of this example was subjected to fourier infrared spectroscopic analysis to successfully prepare a loaded hydrogel.
The prepared hydrogel loaded with hexametaphosphate is soaked in 0.5wt% FeCl 2 Solution and FeCl 3 After the solution, there was a significant precipitation of the complex in the solution, as shown in FIG. 11.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. Use of a supported polymer or a supported hydrogel in a water treatment agent and/or a corrosion and rust inhibitor, characterized in that the supported polymer comprises: a polymer and an anion supported on the polymer;
the polymer comprises at least one electrolyte unit;
the electrolyte unit has a structure shown in a formula (I) or a formula (II);
formula (I); />Formula (II);
wherein R is 1 Quaternary ammonium ion, quaternary phosphonium ion, sulfonium ion, imidazolium ion, pyridinium ion, piperidinium ion, pyrrolidinium ion, or zwitterionic;
R 2 is phenyl, C0-a C20 alkyl group or a C0-C20 alkoxy group;
the compound of the structure shown in the formula (I) does not contain R 3 Or R is 3 Selected from amide groups or ester groups;
R 4 selected from hydrogen or methyl;
R 5 、R 6 each independently selected from methyl, ethyl, or phenyl;
the anions include: multivalent anions and/or monovalent anions;
the polyvalent anions comprise one or more than two of chromate, molybdate, tungstate, vanadate, borate, selenite, hexametaphosphate, phytate, aminotrimethylene phosphonate, ethylenediamine tetraacetate, ethylenediamine tetramethylene phosphonate, hydroxyisomethylene diphosphonate, tripolyphosphate, citrate, maleate and polyacrylate;
the monovalent anions comprise one or more than two of nitrite, nitrate, dodecyl benzene sulfonate, monovalent acid radical of 11-hydroxy undecyl phosphoric acid, monovalent acid radical of dodecyl phosphoric acid, monovalent acid radical of mono-tetradecyl phosphoric acid and monovalent acid radical of mono-hexadecyl phosphoric acid;
the polymer further comprises: at least one non-electrolyte cell;
the non-electrolytic unit includes a non-electrolyte monomer copolymerized with an electrolyte monomer of the electrolyte unit;
the non-electrolyte monomer has the following structure:
；
wherein R is 7 Selected from hydrogen or methyl;
r in the non-electrolyte monomer 8 Is an amide group or an ester group;
R 9 alkyl of C0-C20;
R 15 is amino, cyano, hydroxy, amide bond, ureido,、/>Or (b)；
The supported hydrogel is obtained by crosslinking the supported polymer.
2. The use according to claim 1, wherein the quaternary ammonium ion has the formula: r is R 9 R 10 R 11 N + The general formula of the quaternary phosphine ion is R 9 R 10 R 11 P + The sulfonium ion has a general formula of R 9 R 10 S + ；
Wherein R is 9 Is methyl, ethyl or phenyl, R 10 Is methyl, ethyl or phenyl, R 11 Methyl, ethyl or phenyl;
the zwitterionic groups are:
、/>、/>or (b)；
Wherein a is more than or equal to 1 and less than or equal to 10, b is more than or equal to 1 and less than or equal to 10, c is more than or equal to 1 and less than or equal to 10, and d is more than or equal to 1 and less than or equal to 10.
3. The use according to claim 1, wherein the imidazolium ions are:
、/>、/>、/>or (b)；
The pyridinium ions are:
、/>、/>or->；
The piperidinium ions are:
、/>、/>or->；
The pyrrolidinium ions are:
、/>or->；
Wherein R is 13 、R 14 Is hydrogen, C1-C10 alkyl or C1-C10 alkoxy, and represents a group together with R 2 Is connected to the connecting point of (c).
4. The use according to claim 1, wherein the electrolyte unit is prepared from an electrolyte monomer;
the electrolyte monomer structure includes:
、/>、/>、、/>、/>、、/>、/>、、/>、/>、、/>、/>、and->One or two or more of them;
wherein R is 10 、R 11 、R 12 Each independently selected from methyl, ethyl or phenyl, R 13 Is hydrogen, C1-C10 alkyl or C1-C10 alkoxy.
5. The use according to claim 1, wherein the non-electrolyte monomer structure comprises:
、/>、/>、/>、/>、、/>、/>、/>、、/>、/>、、/>and、/>one or two or more of them;
wherein the above structure does not contain R 9 Or R 9 Alkyl of C1-C20;
R 7 selected from hydrogen or methyl.
6. The use according to claim 1, wherein the ratio of the total number of moles of electrolyte monomers to the total number of moles of non-electrolyte monomers is 1: (5-20).
7. The use according to claim 1, wherein the method of preparing the supported hydrogel comprises steps 1-3 or steps a-b:
step 1: mixing an electrolyte monomer or a precursor of the electrolyte monomer, an initiator, a cross-linking agent, inorganic salt and a solvent to obtain a pre-reaction solution; the solvent is an organic solvent and/or water;
step 2: under the initiation condition, the pre-reaction solution is subjected to polymerization reaction to obtain a polymer;
step 3: transferring the polymer into a mixture with an anionic salt solution, and filtering to obtain a supported hydrogel;
step a: mixing an electrolyte monomer or a precursor of the electrolyte monomer, an initiator, a cross-linking agent, inorganic salt, anionic salt and a solvent to obtain a pre-reaction solution; the solvent is an organic solvent and/or water;
step b: and under the initiation condition, the pre-reaction solution is subjected to polymerization reaction to obtain the supported gel.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104871038A (en) * 2012-12-21 2015-08-26 库柏维景国际控股公司 Silicone hydrogel contact lenses for sustained release of beneficial polymers
GB2527640A (en) * 2014-04-21 2015-12-30 Friedrich Wilhelm Wieland Corrosion inhibitors, improved paint and corrosion protection coating
CN108350305A (en) * 2015-09-21 2018-07-31 朗·里昂 Hydrogel, preparation and the Medical Devices for including the electrode for being coated with hydrogel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104871038A (en) * 2012-12-21 2015-08-26 库柏维景国际控股公司 Silicone hydrogel contact lenses for sustained release of beneficial polymers
GB2527640A (en) * 2014-04-21 2015-12-30 Friedrich Wilhelm Wieland Corrosion inhibitors, improved paint and corrosion protection coating
CN108350305A (en) * 2015-09-21 2018-07-31 朗·里昂 Hydrogel, preparation and the Medical Devices for including the electrode for being coated with hydrogel

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* Cited by examiner, † Cited by third party
Title
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