CN112029103A - Preparation of acid-base ion modified polymer and porous membrane thereof - Google Patents
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- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08J2429/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The invention discloses an acid-base ion modified polymer and a porous membrane prepared by the polymer, wherein the sulfonic group modified hydrophobic polymer has increased brittleness while enhancing hydrophilicity, so that the elongation at break is reduced, and the service life of the membrane is reduced.
Description
Technical Field
The invention belongs to the field of film material research, and particularly relates to an acid-base ion modified polymer and a porous film thereof.
Background
Porous membrane filtration is the earliest membrane technology developed and applied in the world, and natural or artificial high molecular compounds are used as membrane materials. Microfiltration utilizes the sieving mechanism of a porous membrane, allows macromolecules, soluble solids (inorganic salts) and the like to pass through under pressure driving, and retains particles with the diameter of 0.1-10 mu m, such as suspended matters, bacteria, partial viruses and large-size colloids, and is mainly used for a feed water pretreatment system.
The material for preparing the porous membrane is required to have the characteristics of high mechanical strength, good chemical stability, good selectivity, hydrophilicity and the like. The existing hydrophilic material has good hydrophilicity, but has poor mechanical property, weak oxidation resistance and short service life of the prepared membrane. The existing hydrophobic material has the characteristics of high mechanical strength, good chemical stability, good selectivity and the like, but has strong hydrophobicity, is easily polluted by proteins, saccharides and organic humic acid substances, and causes pressure rise, flux reduction and operation energy consumption rise in the operation process.
Most of the resins for preparing the polymer membrane are materials with poor hydrophobicity or hydrophilicity, and the materials need to be modified or modified in order to realize the hydrophilicity or super-hydrophilicity of the porous membrane, so that the performances of pollution resistance, high flux, low resistance and the like are better realized. In the existing modification method, the polymer material has better sulfonation modification effect, the sulfonation modification process has the advantages of simple operation, easy control and the like, and the modified filter membrane has obviously enhanced hydrophilicity due to the strong hydrophilicity of the sulfonic acid group, so that the requirement of the porous membrane on the hydrophilicity can be met.
Although the material modified by sulfonation has good hydrophilicity, the mechanical property of the material is obviously reduced, the oxidation resistance is weakened, and the overall performance of the prepared porous membrane needs to be improved. The main reason is that the physical and mechanical properties of the material are reduced and the elongation at break is reduced due to the damage of the molecular chain or group of the polymer caused by sulfonation modification. The elongation at break of a polymeric material is generally expressed in terms of the relative elongation at break, i.e. the ratio of the elongation at break to its initial length, expressed in percent. It is an index for characterizing the toughness or elasticity properties. A greater elongation at break indicates better toughness or elastic properties. The larger the elongation at break of the prepared porous membrane under pressure, the stronger the impact resistance or processability and the longer the service life.
After common film-forming polymer resin is sulfonated, the elongation at break of a porous film prepared from the film-forming polymer resin is reduced by 10-50%, the service life and the performance of the porous film are greatly influenced, and therefore, on the premise of meeting the hydrophilicity of the material, the elongation at break of the film-forming polymer material is improved, and the flexibility of the material is increased.
Disclosure of Invention
The invention discloses an acid-base ion modified polymer and a porous membrane prepared by the polymer, wherein the sulfonic group modified hydrophobic polymer has enhanced hydrophilicity and reduced toughness, which leads to reduced elongation at break and reduced service life of the membrane.
The technical scheme of the invention is as follows:
an acid-base ion modified polymer comprises a block copolymer of a formula A-B-C, wherein a block A is a hydrophobic polymer chain segment, a block B is a sulfonated polymer chain segment of a substance A, and a block C is a polymer chain segment of the substance B, wherein a sulfonic acid group is modified by a basic ion; the amount of the block A in the polymer is 15-85 mol%, the amount of the block B is 2-65 mol%, and the amount of the block C is 5-75 mol%.
Preferably, the block a is any one of polysulfone, polyarylsulfone, polyethersulfone, polyetherethersulfone, polyphenylene sulfide, polyetheretherketone, polyamide, polyaramide, polyimide, polyvinylidene fluoride, polystyrene, polymethylpentene, and polyamidonitrile.
Furthermore, the sulfonation degree of the block B is 2-75%.
Further, the donor of the basic ion is N, N-dimethyl-1, 3-diaminopropane.
A preparation method of an acid-base ion modified polymer comprises the following steps:
(1) sulfonating a hydrophobic polymer A by using concentrated sulfuric acid as a solvent and bromosulfonic acid or chlorosulfonic acid as a sulfonating agent, wherein the sulfonation degree is 2-75%, and the sulfonated polymer is B;
(2) activating the polymer B by using an activating agent in a solvent, and substituting by using N, N-dimethyl-1, 3-diaminopropane to obtain a polymer C modified by a sulfonic acid group;
(3) polymerizing the substance A, the substance B and the substance C to form the block copolymer of the formula A-B-C.
Preferably, the activator is N-vinylimidazole.
Preferably, the mass fraction of the concentrated sulfuric acid is 75-99%, and the addition amount of the bromosulfonic acid is 10-85 mol% of the polymer A.
Preferably, the amount of the N-vinyl imidazole is 20-75 mol% of the polymer B, and the amount of the N, N-dimethyl-1, 3-diaminopropane is 15-80 mol% of the polymer B.
The invention has the beneficial effects that:
in order to reduce the loss of the elongation at break of the material to the maximum extent, the hydrophobic polymer is sulfonated at a low sulfonation degree of 2-75%, at the moment, the hydrophilic performance of the material meets the requirement of the filter membrane on the fluid flux, and the loss of the elongation at break of the material is small.
The block A is a hydrophobic polymer chain segment, and the mechanical strength, the chemical stability and the good selectivity of the material are reserved; the block B is a sulfonated polymer chain segment of the block A, and the block A is sulfonated at a low sulfonation degree, so that the material has hydrophilicity, the adsorption effect of the surface of the membrane and pollutants such as protein or colloid can be reduced, the pollution of the membrane is greatly reduced, the service life of the membrane is prolonged, and the biocompatibility of the membrane is improved; the block C is a polymer chain segment obtained by modifying a sulfonic acid group with a basic ion in the block B, and the material is crosslinked into a net shape for enhancing the toughness of the material so as to make up for the defect that the elongation at break of the sulfonated material is reduced.
The porous membrane prepared by the polymer has the advantages of enhanced affinity between the membrane and water, uniform pore diameter, high filtration precision, large porosity, strong machinery, pollution resistance, long service life and the like. Under the same pressure, the method has higher permeation flux, improves the separation efficiency and reduces the energy consumption and the operation cost.
Detailed Description
Example 1
Preparation of block B: the block A is polyether sulfone, and the block B is obtained after the polyether sulfone is sulfonated.
Weighing 50g of polyether sulfone, placing the polyether sulfone into a 2500mL three-neck flask, slowly adding 500mL of 90% sulfuric acid into the three-neck flask while stirring to completely dissolve the polyether sulfone in a sulfuric acid solution, after the solution is uniform, controlling the temperature to be 25 ℃, dropwise adding bromosulfonic acid into the three-neck flask at a certain stirring speed, wherein the dropwise adding speed is 2 drops/second, continuously stirring for 2 hours after dropwise adding for 1 hour, pouring a reaction mixture onto a glass plate to form a film, washing with deionized water for 3 times, washing off residual sulfuric acid on the film, and drying in an oven at 120 ℃ for 1 hour to obtain the sulfonated polyether sulfone.
The sulfonation degree of sulfonated polyether sulfone is detected, 1.0g of sulfonated polyether sulfone is precisely weighed, 20mL of dimethylformamide is added for dissolution, 0.0914mol/L of standard NaOH solution is used for titration, the sulfonation degree is measured, and the sulfonation degree of the substance B obtained in example 1 is 10% through measurement.
Example 2
Another preparation process for the block B: the block A is polysulfone, and the block B is obtained after the polysulfone is sulfonated.
Weighing 50g of polysulfone, placing the polysulfone into a 2500mL three-neck flask, slowly adding 500mL of 90% sulfuric acid into the three-neck flask while stirring to completely dissolve the polysulfone in a sulfuric acid solution, after the solution is uniform, controlling the temperature to be 25 ℃, dropwise adding bromosulfonic acid into the three-neck flask at a certain stirring speed, wherein the dropwise adding speed is 2 drops/second, dropwise adding for 1.5 hours, continuously stirring for 2 hours, pouring the reaction mixture onto a glass plate to form a film, washing with deionized water for 3 times, washing off the residual sulfuric acid on the film, and drying in an oven at 100 ℃ for 2 hours to obtain the sulfonated polysulfone.
The sulfonation degree of sulfonated polysulfone is detected, 1.0g of sulfonated polyether sulfone is precisely weighed, 20mL of dimethylformamide is added for dissolution, 0.0914mol/L of standard NaOH solution is used for titration, the sulfonation degree is measured, and the sulfonation degree of the substance B obtained in example 1 is 14% through measurement.
Example 3
Another preparation process for the block B: the block A is polyether-ether-ketone, and the block B is obtained after the polyether-ether-ketone is sulfonated.
Weighing 50g of polyether-ether-ketone, placing the polyether-ether-ketone into a 2500mL three-neck flask, slowly adding 500mL of 90% sulfuric acid into the three-neck flask while stirring to completely dissolve the polyether-ether-ketone in a sulfuric acid solution, after the solution is uniform, controlling the temperature to be 25 ℃, dropwise adding bromosulfonic acid into the three-neck flask at a certain stirring speed, wherein the dropwise adding speed is 2 drops/second, continuously stirring for 2 hours after dropwise adding, pouring the reaction mixture onto a glass plate to form a film, washing with deionized water for 3 times, washing off the residual sulfuric acid on the film, and drying in an oven at 90 ℃ for 6 hours to obtain the sulfonated polyether-ether-ketone.
The sulfonation degree of sulfonated polyether ether ketone is detected, 1.0g of sulfonated polyether ether ketone is precisely weighed, 20mL of diphenyl sulfoxide is added for dissolution, 0.0914mol/L of standard NaOH solution is used for titration, the sulfonation degree is measured, and the sulfonation degree of the substance B obtained in example 1 is 19% through measurement.
Example 4
And the preparation method of the block C is characterized in that sulfonated polyether sulfone is modified by N, N-dimethyl-1, 3-diaminopropane.
Dissolving 30g of sulfonated polyether sulfone into 200mL of dimethylformamide, fully stirring to completely dissolve the sulfonated polyether sulfone, pouring the mixture into a three-neck flask with a stirrer, adding 4.15g of N-vinylimidazole, stirring for 3.5 hours at 55 ℃, adding 3.12g of N, N-dimethyl-1, 3-diaminopropane into the three-neck flask, further stirring for 3.0 hours at 55 ℃, after that, pouring the mixture in the three-neck flask into clear water, washing the obtained precipitate for 3 times by deionized water after filtering, drying for 12 hours in an oven at 50 ℃, dissolving the obtained precipitate into 100mL of dimethyl sulfoxide, casting on a clean glass plate, and drying for 12 hours in the oven at 50 ℃.
Example 5
Another preparation method of the block C is that the sulfonated polysulfone is modified with N, N-dimethyl-1, 3-diaminopropane.
Dissolving 30g of sulfonated polysulfone into 200mL of dimethylacetamide, fully stirring to completely dissolve the sulfonated polysulfone, pouring the mixture into a three-neck flask with a stirrer, adding 5.10g of N-vinylimidazole, stirring for 3.5 hours at 55 ℃, adding 4.22g of N, N-dimethyl-1, 3-diaminopropane into the three-neck flask, further stirring for 3.0 hours at 55 ℃, after that, pouring the mixture in the three-neck flask into clear water, washing the obtained precipitate for 3 times by deionized water after filtering, drying for 12 hours in an oven at 50 ℃, dissolving the obtained precipitate into 100mL of dimethylacetamide, casting on a clean glass plate, and drying for 12 hours in the oven at 50 ℃.
Example 6
In another method for preparing block C, the sulfonated polyetheretherketone is modified with N, N-dimethyl-1, 3-diaminopropane.
Dissolving 30g of sulfonated polyether ether ketone into 200mL of dimethyl sulfoxide, neutralizing, fully stirring to completely dissolve the sulfonated polyether ether ketone, pouring the mixture into a three-neck flask with a stirrer, adding 5.90g of N-vinyl imidazole, stirring for 3.5 hours at 55 ℃, adding 5.12g of N, N-dimethyl-1, 3-diaminopropane into the three-neck flask, further stirring for 3.0 hours at 55 ℃, pouring the mixture in the three-neck flask into clear water after the stirring is finished, washing the obtained precipitate for 3 times by using deionized water after filtering, drying for 12 hours in an oven at 50 ℃, dissolving the obtained precipitate into 100mL of dimethyl sulfoxide, casting on a clean glass plate, and drying for 12 hours in the oven at 50 ℃.
Example 7
The preparation method of the block polymer A-B-C comprises the following steps:
adding 6.0mol% of polyether sulfone into 250mL of N-methyl-2-pyrrolidone in a 500mL flask with a stirrer, heating to 90-120 ℃, fully stirring to completely dissolve polyether ketone in a solvent, adding 2g of potassium hydroxide into the flask, continuously stirring for 10min to ensure that the mixture is uniform, adding 1.0mol of sulfonated polyether sulfone, continuously stirring for 1 h, then adding 2.0mol of C substance, and keeping the reaction mixture at 100 ℃ for 10 h. The reaction mixture was quenched by the addition of 30mL of acetic acid and allowed to cool to room temperature. The mixture in the flask was poured slowly into 200mL of acetone, precipitating the product. The precipitate was filtered through a buchner filter and washed with 200mL acetone and 500mL water, respectively, and the precipitate was dried in an oven at 90 ℃ for 6 hours to give a dried product as a white solid powder containing 5.7mol% of substance a, 0.9mol% of substance B, and 1.9mol% of substance C as determined by NMR.
Preparing a film casting solution, wherein the film forming resin content is 30 percent, the polyvinyl alcohol 200 content is 5 percent and the balance is solvent dimethylformamide according to the weight percentage, and fully stirring and dissolving the film casting solution at the temperature of 100 ℃; placing the film-casting solution in an oven at 50 ℃ for standing and degassing for more than 24 hours until the bubbles in the film-casting solution are completely removed; and (3) uniformly coating the casting solution on a glass plate in a certain warm and humid environment to obtain a primary membrane, immersing the primary membrane in pure water, soaking and washing for 8 hours, and then putting the primary membrane in a 90 ℃ oven for drying and shaping to obtain the modified polysulfone porous membrane. Through tests, the water contact angle of the modified polyether sulfone porous membrane is 13 degrees, the water permeability is 15 ml/square centimeter/min/kg, the explosion pressure is more than 0.11 MPa, the mechanical tensile strength is more than 650 cN/15 mm, and the elongation at break is 29 percent.
Example 8
Another preparation method of the block polymer A-B-C comprises the following steps:
in a 500mL flask equipped with a stirrer, 5mol% polysulfone was added to 250mL of N-methyl-2-pyrrolidone, the mixture was heated to 90-100 ℃, polysulfone was completely dissolved in the solvent by sufficient stirring, 2g of potassium hydroxide was added to the flask, the mixture was homogenized after continuing stirring for 10min, 1.5mol% sulfonated polysulfone (the product of example 2) was added thereto, the mixture was further stirred for 1 hour, 2.5mol% C substance (the product of example 4) was added thereto, and the reaction mixture was kept at 100 ℃ for 10 hours. The reaction mixture was quenched by the addition of 30mL of acetic acid and allowed to cool to room temperature. The mixture in the flask was poured slowly into 200mL of acetone, precipitating the product. The precipitate was filtered through a buchner filter and washed with 200mL acetone and 500mL water, respectively, and the precipitate was dried in an oven at 80 ℃ for 12 hours to give a dried product as a white solid powder containing 4.8mol% of substance a, 1.4mol% of substance B, and 2.3mol% of substance C as determined by NMR.
Preparing a film casting solution, wherein the content of film forming resin is 25 percent, the content of polyvinyl alcohol 200 is 5 percent and the balance is solvent dimethylacetamide according to the weight percentage, and fully stirring and dissolving the film casting solution at the temperature of 100 ℃; placing the film-casting solution in an oven at 50 ℃ for standing and degassing for more than 24 hours until the bubbles in the film-casting solution are completely removed; and (3) uniformly coating the casting solution on a glass plate in a certain warm and humid environment to obtain a primary membrane, immersing the primary membrane in pure water, soaking and washing for 12 hours, and then putting the primary membrane in a 70 ℃ hot air oven for drying and shaping to obtain the modified polysulfone porous membrane. Through tests, the water contact angle of the modified polysulfone porous membrane is 17 degrees, the water permeability is 15 ml/square centimeter/min/kg, the bursting pressure is more than 0.13 MPa, the mechanical tensile strength is more than 700 cN/15 mm, and the elongation at break is 22 percent.
Example 9
Another preparation method of the block polymer A-B-C comprises the following steps:
in a 500mL flask with a stirrer, 4mol% of polyetheretherketone was added to 250mL of N-methyl-2-pyrrolidone, heated to 95 ℃, polyetheretherketone was completely dissolved in the solvent by thorough stirring, 2g of potassium hydroxide was added to the flask, after stirring for 10min was continued, the mixture was homogenized, 2.0mol% of sulfonated polyetheretherketone (using the product of example 3) was added, after stirring for 1 hour was continued, 3.0mol% of substance C (using the product of example 6) was added, and the reaction mixture was kept at 100 ℃ for 10 hours. The reaction mixture was quenched by the addition of 30mL of acetic acid and allowed to cool to room temperature. The mixture in the flask was poured slowly into 200mL of acetone, precipitating the product. The precipitate was filtered through a buchner filter and washed with 200mL acetone and 500mL water, respectively, and the precipitate was dried in an oven at 80 ℃ for 12 hours to give a dried product as a white solid powder containing 3.9mol% of substance a, 1.9mol% of substance B, and 2.8mol% of substance C as determined by NMR.
Preparing a film casting solution, wherein the content of film forming resin is 20 percent, the content of polyvinyl alcohol 200 is 5 percent and the balance is solvent dimethyl sulfoxide according to the weight percentage, and fully stirring and dissolving the film casting solution at the temperature of 100 ℃; placing the film-casting solution in an oven at 50 ℃, standing and degassing for more than 24 hours until the bubbles in the film-casting solution are completely removed; and (3) uniformly coating the casting film liquid on a glass plate in a certain warm and humid environment to obtain a primary film, immersing the primary film in pure water, soaking and washing for 24 hours, and then putting the primary film in a hot air oven at 120 ℃ for drying and shaping to obtain the modified polyether-ether-ketone porous film. Through tests, the water contact angle of the modified polyether-ether-ketone porous membrane is 14 degrees, the water permeability is 18 ml/square centimeter/min/kg, the explosion pressure is more than 0.11 MPa, the mechanical tensile strength is more than 500 cN/15 mm, and the elongation at break is 26 percent.
The introduction of the sulfonated group into the polymer can enhance the hydrophilicity of the filter membrane and effectively reduce the microfiltration and filtration resistance. However, the modified resin has too strong hydrophilicity, which causes the mechanical property of the membrane to be reduced, the mechanical strength of the membrane product is gradually reduced, the elongation at break is reduced, the toughness becomes poor and becomes brittle, and the problem that the elongation at break of the material is reduced can be effectively improved after the sulfonic acid group is modified by the alkali group, and the elongation at break is more than 20 percent in the above cases, so that the material modified by the alkali group has good toughness, and the service life of the filter membrane can be effectively prolonged.
The above examples are only intended to illustrate the technical solution and innovative idea of the present invention, and not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, those skilled in the art will appreciate that; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions and improvements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. An acid-base ion modified polymer, comprising:
a block copolymer of the formula A-B-C,
wherein, the block A is an aromatic hydrophobic polymer chain segment, the block B is a sulfonated polymer chain segment of the substance A, and the block C is a polymer chain segment of the substance B after a sulfonic acid group is modified by basic ions;
the amount of the block A in the polymer is 15-85 mol%, the amount of the block B is 5-65 mol%, and the amount of the block C is 5-75 mol%.
2. The acid-base ion modified polymer according to claim 1, wherein the block A is any one of polyethersulfone, polysulfone, polyarylsulfone, polyetherketone, polyetheretherketone, polyvinylidene fluoride, polyamide, polyaramid, polyimide, polyacrylonitrile, polymethylpentene, and cellulose.
3. The acid-base ion modified polymer according to claim 1, wherein the sulfonation degree of the block B is 2 to 75%.
4. The acid-base ion modified polymer of claim 1, wherein the donor of the basic ion is N, N-dimethyl-1, 3-diaminopropane.
5. The method for preparing the acid-base ion modified polymer according to any one of claims 1 to 4, comprising the steps of:
sulfonating a hydrophobic polymer A by using concentrated sulfuric acid as a solvent and bromosulfonic acid or chlorosulfonic acid as a sulfonating agent, wherein the sulfonation degree is 2-75%, and the sulfonated polymer is B;
activating the polymer B by using an activating agent in a solvent, and substituting by using N, N-dimethyl-1, 3-diaminopropane to obtain a polymer C modified by a sulfonic acid group;
polymerizing the substance A, the substance B and the substance C to form the block copolymer of the formula A-B-C.
6. The acid-base ion modified polymer of claim 5, wherein the activator is N-vinylimidazole.
7. The acid-base ion modified polymer according to claim 6, wherein the mass fraction of the concentrated sulfuric acid is 75 to 99%, and the addition amount of the bromosulfonic acid or chlorosulfonic acid is 10 to 70mol% of the polymer A.
8. The acid-base ion modified polymer according to claim 6, wherein the amount of N-vinylimidazole is 20 to 75mol% and the amount of N, N-dimethyl-1, 3-diaminopropane is 15 to 80mol% based on the polymer B.
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